US7879994B2 - Cellulose interpolymers and method of oxidation - Google Patents

Cellulose interpolymers and method of oxidation Download PDF

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US7879994B2
US7879994B2 US10/995,750 US99575004A US7879994B2 US 7879994 B2 US7879994 B2 US 7879994B2 US 99575004 A US99575004 A US 99575004A US 7879994 B2 US7879994 B2 US 7879994B2
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cellulose
cellulose ester
ester interpolymer
oxidized
acid
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US20050192434A1 (en
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Charles Michael Buchanan
Norma Lindsey Buchanan
Susan Northrop Carty
Chung-Ming Kuo
Juanelle Little Lambert
Jessica Dee Posey-Dowty
Thelma Lee Watterson
Matthew Davie Wood
Michael Orlando Malcolm
Margaretha Soderqvist Lindblad
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Eastman Chemical Co
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Eastman Chemical Co
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Priority to US12/975,440 priority patent/US8816066B2/en
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Priority to US13/728,258 priority patent/US9243072B2/en
Priority to US13/728,153 priority patent/US9150665B2/en
Priority to US13/728,216 priority patent/US9040685B2/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/06—Cellulose acetate, e.g. mono-acetate, di-acetate or tri-acetate
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
    • A61K47/38—Cellulose; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/20—Pills, tablets, discs, rods
    • A61K9/2004—Excipients; Inactive ingredients
    • A61K9/2022—Organic macromolecular compounds
    • A61K9/205—Polysaccharides, e.g. alginate, gums; Cyclodextrin
    • A61K9/2054—Cellulose; Cellulose derivatives, e.g. hydroxypropyl methylcellulose
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/4891—Coated capsules; Multilayered drug free capsule shells
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • C08B15/04—Carboxycellulose, e.g. prepared by oxidation with nitrogen dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/04—Cellulose formate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/08—Preparation of cellulose esters of organic acids of monobasic organic acids with three or more carbon atoms, e.g. propionate or butyrate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/16—Preparation of mixed organic cellulose esters, e.g. cellulose aceto-formate or cellulose aceto-propionate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/22—Post-esterification treatments, including purification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B3/00—Preparation of cellulose esters of organic acids
    • C08B3/22—Post-esterification treatments, including purification
    • C08B3/24—Hydrolysis or ripening
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/12—Cellulose acetate
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C08L1/14—Mixed esters, e.g. cellulose acetate-butyrate
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/14—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles
    • A61K9/19—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles lyophilised, i.e. freeze-dried, solutions or dispersions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/20—Pills, tablets, discs, rods
    • A61K9/28—Dragees; Coated pills or tablets, e.g. with film or compression coating
    • A61K9/2806—Coating materials
    • A61K9/2833—Organic macromolecular compounds
    • A61K9/286—Polysaccharides, e.g. gums; Cyclodextrin
    • A61K9/2866—Cellulose; Cellulose derivatives, e.g. hydroxypropyl methylcellulose

Definitions

  • This invention provides cellulose ester interpolymers, cellulose interpolymers, and methods of oxidizing cellulose interpolymers and cellulose ester interpolymers.
  • Cellulose esters are well known compounds (“Cellulose Derivatives”, Ben P. Rouse, Kirk-Othmer Encyclopedia of Chemical Technology, vol 4, 1964, 616-683).
  • the most common cellulose esters are comprised of aliphatic C 2 -C 4 substitutents. Examples of such cellulose esters include cellulose acetate (CA), cellulose propionate (CP), cellulose butyrate (CB), cellulose acetate propionate (CAP), and cellulose acetate butyrate (CAB).
  • CA cellulose acetate
  • CP cellulose propionate
  • CB cellulose butyrate
  • CAP cellulose acetate propionate
  • CAB cellulose acetate butyrate
  • Examples of the utility of such cellulose esters can be found in Prog. Polym. Sci. 2001, 26, 1605-1688.
  • Cellulose esters are generally prepared by first converting cellulose to a cellulose triester before hydrolyzing the cellulose triester in an acidic aqueous media to the desired degree of substitution (DS, the number of substitutents per anhydroglucose monomer).
  • DS degree of substitution
  • Aqueous acid catalyzed hydrolysis of cellulose triacetate yields a random copolymer that can consist of 8 different monomers depending upon the final DS (Macromolecules 1991, 24, 3050).
  • regioselective substitution means the exclusive or preferential placement or removal of a substituent at the C2, C3, or C6 hydroxyls of the anhydroglucose monomer of cellulose. Controlled placement of the substituent can lead to a homopolymer or a copolymer of cellulose with specific monomer content. That is, a cellulose derivative with a specific substitution pattern within the anhydroglucose monomer and a controlled sequence along the cellulose polymer chain is obtained.
  • carboxylated cellulose esters Only a few classes of carboxylated cellulose esters are known.
  • One example of this class of cellulose ester derivatives is carboxymethyl cellulose esters described for example in U.S. Pat. Nos. 5,668,273; 5,792,856; and 5,994,530.
  • These cellulose derivatives are cellulose ether esters in which an intervening ether linkage attaches a carboxylate to the anhydroglucose units of the cellulose chain. These derivatives are formed by esterifying carboxymethyl cellulose (an ether) to the fully substituted carboxymethyl cellulose ester followed by hydrolysis to the desired ester DS.
  • This class of carboxylated cellulose esters offers the advantage of a non-hydrolysable carboxylate linkage.
  • the disadvantage is that the method of preparation is a two-step process requiring the preparation and isolation of the carboxymethyl cellulose prior to esterification. Furthermore, one cannot obtain a consistent, homogeneous distribution of carboxymethyl
  • carboxylated cellulose esters are those in which the carboxylate functionality is attached to the cellulose backbone via an ester linkage.
  • An example of this class is cellulose acetate phthalate and the like which are described in U.S. Pat. No. 3,489,743.
  • these cellulose ester derivatives are formed by first preparing a neutral, randomly substituted cellulose ester, e.g. a CA, with the desired DS.
  • the carboxylate functionality is installed by treating the cellulose ester with an anhydride such as phthalic anhydride.
  • carboxylated cellulose esters are those, which result from ozonolysis of cellulose esters in the solid state (Sand, I. D., Polymer Material Science Engineering, 1987, 57-63; U.S. Pat. No. 4,590,265).
  • Ozonolysis of cellulose ester provides a polymer that contains not only carboxylates but also aldehydes, ketone, and peroxides as well. The process results in significant loss in polymer molecular weight and relatively low levels of oxidation. Furthermore, the process is not specific in that any of the cellulose ester hydroxyls can be oxidized.
  • Oxidation of carbohydrates and polysaccharides is a very important process in the chemical industry and a number of useful catalysts for this transformation have been developed. Some of the most useful catalysts belong to the class of compounds referred to as nitroxyl or nitroxide radicals. Typically, these compounds are secondary amine nitroxides with the general structure shown below.
  • Oxidation of alcohols with TEMPO under acidic conditions converts primary and secondary alcohols to aldehydes and ketones, respectively (Bobbit, J. M.; Ma, Z., J. Org. Chem. 1991, 56, 6110-6114). Generally, over oxidation is not observed, but two molar equivalents of TEMPO per mole of substrate are required for the oxidation of the alcohol. That is, the reaction is not catalytic.
  • TEMPO catalyzed oxidations of primary alcohols in nonaqueous reaction media under acidic conditions can give almost exclusively the corresponding aldehyde.
  • aqueous media some subsequent conversion of the aldehyde to a carboxylate is observed, but the aldehyde to carboxylic acid ratio remains high.
  • oxidation of primary alcohols of polysaccharides and carbohydrates under acidic conditions using prior art TEMPO catalyzed conditions is of limited utility due to the fact that the extent of oxidation is limited and the reaction media is not suitable for many substrates.
  • Typical pH and temperature for TEMPO catalyzed oxidation of polysaccharides, such as starch, are in the range of 8.5-11.5 at a temperature of ⁇ 10 to 25° C.
  • Oxidation of polysaccharides and carbohydrates under alkaline conditions using analogues of TEMPO and other primary oxidants has also been investigated (Carbohydrate Research 2000, 328, 355-363; J. Mol. Catal. A: Chem. 2001, 170, 35-42; J. Catal. 2000, 194, 343-351; Proc. Electrochem. Soc. 1993, 260-7; Carbohydr. Res. 1995, 268, 85-92; EP 0979826 A1; U.S. Pat. No. 5,831,043; U.S. 2001/0034442 A1).
  • the present invention provides cellulose ester interpolymers wherein the C2 and C3 positions of each of the anhydroglucose units of the cellulose ester interpolymer are in the alcohol oxidation state, and comprising anhydroglucose units
  • R 1 , R 2 , R 3 , R 4 , and R 5 are independently selected from the group consisting of hydrogen and C 2 -C 12 acyl groups, wherein at least one of R 1 , R 2 , R 3 , R 4 , and R 5 is a C 2 -C 12 acyl group; and, X is formyl, hydroxymethylene, aminomethyl, R 6 —NH—CH 2 — or carboxy or a mixture thereof, wherein R 6 is selected from the group consisting of alkyl, aryl, or alkylene-aryl, provided when at least some of X is carboxy, the acid number is greater than 10; wherein the anhydroglucose units A and B comprise greater than 65% of the total anhydroglucose units of the cellulose portion of the cellulose ester interpolymer.
  • the present invention provides cellulose ester interpolymers comprising a plurality of anhydroglucose units having a C6 carboxy group and wherein the cellulose ester interpolymer has an apparent degree of substitution per anhydroglucose unit of C 2 -C 12 acyl of at least about 0.6 and an acid number of greater than 10.
  • the present invention provides oxidized cellulose interpolymers having a degree of polymerization of at least 10, an acid number of greater than 10, and a random distribution throughout the cellulose interpolymer of anhydroglucose units having a C6 carboxy group.
  • the present invention provides cellulose ester interpolymers comprising anhydroglucose units
  • R 1 , R 2 , R 3 , R 4 , and R 5 are independently selected from the group consisting of C 2 -C 12 acyl groups; X is hydroxymethyl; and wherein the anhydroglucose units A and B comprise greater than 65% of the total anhydroglucose units of the cellulose portion of the cellulose ester interpolymer, and the degree of substitution per anhydroglucose unit of C 2 -C 12 acyl groups is from about 1.5 to about 2.5.
  • the present invention provides cellulose ester interpolymers having a degree of substitution per anhydroglucose unit of formate of 0.5 to 1.3, and a degree of substitution of C 2 -C 12 acyl of 1.5 to 2.5.
  • the present invention provides a method for converting a C6 hydroxyl of an anhydroglucose unit of cellulose polymer to a formyl group or a carboxyl group comprising: adding an amino substituted cyclic nitroxyl derivative, a primary oxidant, and a terminal oxidant to a cellulose mixture having a pH of less than 4 to form a reaction mixture, wherein the cellulose mixture comprises a C 2 -C 12 alkyl acid, water, and a cellulose polymer comprising anhydroglucose units having C6 hydroxyl groups; and passing of a reaction period sufficient to effect conversion of a C6 hydroxyl to a formyl group or a carboxy group and thus produce an oxidized cellulose interpolymer.
  • the above process further comprising reacting the oxidized cellulose interpolymer with a C 2 -C 12 acyl anhydride or a mixture thereof.
  • the present invention provides a method for converting a C6 hydroxyl of an anhydroglucose unit of a cellulose ester interpolymer to a formyl group or a carboxyl group comprising: adding an amino substituted cyclic nitroxyl derivative, a primary oxidant, and a terminal oxidant to a cellulose mixture having a pH of less than 4 to form a reaction mixture, wherein the cellulose mixture comprises a C 2 -C 12 alkyl acid, water, and a cellulose ester interpolymer comprising anhydroglucose units having C6 hydroxyl groups; and passing of a reaction period sufficient to effect conversion of a C6 hydroxyl to a formyl group or a carboxy group and thus produce an oxidized cellulose ester interpolymer.
  • a method for preparing a stable form of a cellulose formate ester interpolymer comprising: (1) mixing formic acid, water, and an C 2 -C 12 acyl anhydride to form a mixed anhydride mixture at a first contact temperature; (2) contacting the mixed anhydride mixture and a cellulose compound to form a reaction mixture at a second contact temperature; (3) adding an acid catalyst to the reaction mixture; (4) passing of a formylation period; wherein a resulting cellulose formate ester interpolymer has a degree of substitution per anhydroglucose unit of formate of about 0.5 to about 1.5.
  • a method for preparing a stable form of a cellulose ester interpolymer comprising: (1) mixing formic acid, water, and an C 2 -C 12 acyl anhydride to form a mixed anhydride mixture at a first contact temperature; (2) contacting the mixed anhydride mixture and a cellulose compound to form a reaction mixture at a second contact temperature; (3) adding an acid catalyst to the reaction mixture; (4) passing of a formylation period; (5) adding a C 2 -C 12 acyl anhydride to the reaction mixture; (6) heating the reaction mixture to a third contact temperature; (7) passing of an acylation period; wherein a resulting cellulose ester interpolymer has a degree of substitution per anhydroglucose unit of C 2 -C 12 acyl of about 1.5 to about 2.5, and a degree of substitution per anhydroglucose unit of formate of about 0.5 to about 1.5.
  • the present invention provides a method for converting a primary alcohol to a formyl, carboxylate, or mixture thereof, comprising: adding a 4-substituted piperidine nitroxyl derivative wherein the substitutent is capable of hydrogen bonding, a primary oxidant, and a terminal oxidant to a mixture to form a reaction mixture, wherein the mixture has a pH of less than about 4 and comprises a compound comprising a primary alcohol functional group; passing of a reaction period sufficient to effect conversion of the primary alcohol functional group.
  • the primary oxidant is a Mn (III) salt.
  • the present invention provides a coating composition
  • a coating composition comprising anionic, cationic, or zwitterionic C 2 -C 12 cellulose ester interpolymers; resins; organic solvents; and, optionally, pigments.
  • the present invention provides a waterborne coating composition
  • a waterborne coating composition comprising anionic, cationic, or zwitterionic C 2 -C 12 cellulose ester interpolymers; resins; organic solvents; water; base; and, optionally, pigments.
  • the present invention provides a drug delivery composition
  • a drug delivery composition comprising anionic, cationic, or zwitterionic C 2 -C 12 cellulose ester interpolymers and a therapeutically active agent.
  • the present invention provides a therapeutic composition
  • a therapeutic composition comprising anionic, cationic, or zwitterionic C 2 -C 12 cellulose ester interpolymers wherein the oxidized cellulose ester is an effective agent in decreasing or preventing the frequency of transmission of the human immunodeficiency virus, herpes viruses, or sexually transmitted bacterial infections.
  • the present invention provides a thermoplastic composition
  • a thermoplastic composition comprising anionic, cationic, or zwitterionic C 2 -C 12 cellulose ester interpolymers thermoplastic compatibilizers; one or more cellulose esters; a polymer; and, optionally, natural fibers.
  • the present invention provides a composite comprising anionic, cationic, or zwitterionic C 2 -C 12 cellulose ester interpolymers thermoplastic compatibilizers; one or more neutral cellulose esters; and natural fibers.
  • the present invention provides a personal care composition
  • a personal care composition comprising anionic, cationic, or zwitterionic C 2 -C 12 cellulose ester interpolymers; resins; solvents; additives; and, optionally, pigments.
  • FIG. 1 is a scheme showing various synthetic routes.
  • FIG. 2 is a graph showing the degree of substitution of formate per anhydroglucose unit as a function of time during a hydrolysis reaction.
  • FIG. 3 is a collection of 13 C NMR spectra of C6 carbon resonances for Examples 20-23.
  • FIG. 4 is a collection of 1 H NMR spectra of cellulose ester interpolymers described in Examples 1-4.
  • FIG. 5 is a plot of dissolution versus time (minutes) for aspirin in compressed tablets with oxidized cellulose acetate at pH 1.2 and 6.8 at 37° C.
  • FIG. 6 shows the dissolution of aspirin from coated capsules at 37° C. at pH 1.2 and pH 6.8.
  • FIG. 7 shows the dissolution of poorly water-soluble drugs from oxidized cellulose acetate:drug mixtures.
  • Ranges may be expressed herein as from “about” one particular value and/or to “about” or another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another aspect.
  • one object of the invention is to form a fully substituted cellulose ester or mixed ester.
  • substituents or reaction conditions one can remove part or all of the acyl substituent attached to the C6 primary hydroxyl.
  • suitable catalysts and oxidants one can oxidize the cellulose ester in a mixture of carboxylic acid and water while maintaining the DS and molecular weight.
  • the aldehyde (III) shown in FIG. 1 is a critical intermediate. By selection of suitable reaction conditions, the aldehyde may be oxidized to the carboxylate (IV) shown in FIG. 1 .
  • the cellulose triesters to be hydrolyzed and oxidized in the present invention can have three substitutents selected independently from alkanoyls having from 2 to 10 carbon atoms.
  • Examples of cellulose triesters include cellulose triacetate, cellulose tripropionate, and cellulose tributyrate or mixed triesters of cellulose such as cellulose acetate propionate, and cellulose acetate butyrate.
  • These cellulose esters can be prepared by a number of methods known to those skilled in the art.
  • cellulose esters can be prepared by heterogeneous acylation of cellulose in a mixture of carboxylic acid and anhydride in the presence of a catalyst such as H 2 SO 4 .
  • Cellulose triesters can also be prepared by the homogeneous acylation of cellulose dissolved in an appropriate solvent such as LiCl/DMAc or LiCl/NMP.
  • cellulose triesters also encompasses cellulose esters that are not completely substituted with acyl groups.
  • cellulose triacetate commercially available from Eastman Chemical Company, Inc., Kingsport, Tenn., U.S.A., typically has a DS from about 2.85 to about 2.95.
  • cellulose triesters useful for the present invention means a cellulose ester having DS of at least 2.85.
  • acyl substitutents After esterification of the cellulose to the triester, part of the acyl substitutents are removed by hydrolysis or by alcoholysis to give a secondary cellulose ester.
  • the distribution of the acyl substituents can be random or non-random.
  • Secondary cellulose esters can also be prepared directly with no hydrolysis by using a limiting amount of acylating reagent. This process is particularly useful when the reaction is conducted in a solvent that will dissolve cellulose. All of these methods yield cellulose esters that are useful for preparing oxidized cellulose esters.
  • the secondary cellulose esters useful in the present invention have a weight average molecular weight (Mw) from about 5,000 to about 400,000 as measured by GPC. In a further embodiment, the Mw is from about 10,000 to about 300,000. In yet a further embodiment, the Mw is from about 25,000 to about 250,000. In one embodiment, the DS of the cellulose esters useful herein is from about 0.5 to about 2.8. In a further embodiment, the DS is from about 1.7 to about 2.7.
  • the most common commercial secondary cellulose esters are prepared by initial acid catalyzed heterogeneous acylation of cellulose to form the cellulose triester. After a homogeneous solution in the corresponding carboxylic acid of the cellulose triester is obtained, the cellulose triester is then subjected to hydrolysis until the desired degree of substitution is obtained. After isolation, a randomly secondary cellulose ester is obtained. That is, the relative degree of substitution (RDS) at each hydroxyl is roughly equal.
  • RDS relative degree of substitution
  • the degree by which a cellulose ester can be oxidized is determined by the amount of C6 hydroxyl that is available for oxidation. In this sense, a randomly substituted cellulose ester limits the level of oxidation that can be achieved. Hence, it would be advantageous to have a method that would provide cellulose esters with a high content of C6 hydroxyl.
  • regioselective substituted cellulose esters can be easily and rapidly prepared by first treating the cellulose with formic anhydride or the mixed formic anhydride prepared in situ from formic acid and acyl anhydride. A second anhydride or mixture of anhydrides is added and the reaction is continued until a triester with the desired molecular weight is formed.
  • the formate ester is stable and can be isolated and characterized at this stage.
  • the triester is principally composed of two monomers: the 6-O-formate-2,3-O-acyl substituted monomer and the 2,3,6-O-acyl substituted monomer.
  • the cellulose formate ester is not isolated but is treated with water or an alcohol in such a manner to selectively remove the formate substitutent without affecting the other acyl substitutents.
  • a regioselective substituted cellulose ester is obtained with a higher level of C6 hydroxyl relative to the known methods.
  • the cellulose ester is principally composed of two monomers: the 2,3-O-acyl substituted monomer and the 2,3,6-O-acyl substituted monomer. It is preferred that the ratio of 2,3-O-acyl substituted monomer to the 2,3,6-O-acyl substituted monomer be at least 0.67, i.e., at least about 40% of the 2,3-O-acyl substituted monomer.
  • the cellulose that can be used in the regioselective reaction can come from a number of sources.
  • useful cellulose include cellulose from wood pulp, bacterial cellulose, or cellulose from annual plants such as cotton or corn.
  • water or another agent to activate, i.e. disrupt the hydrogen bonding of the cellulose, prior to esterification.
  • those skilled in the art will recognize it may be preferential to activate the cellulose prior to esterification.
  • the formic acid that can be used to make the formic anhydride or the mixed formic anhydride is commercially available and typically contains 1-15% H 2 O.
  • Formic acid and formic anhydride are inherently not stable and the H 2 O serves to stabilize the formic acid.
  • an equal molar or slight excess amount of acyl anhydride, based on moles of water is added to the aqueous formic acid.
  • the preferred acyl anhydride contains 2-12 carbon atoms.
  • the preferred acyl anhydrides are acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, or a mixture thereof.
  • the preferred temperature is from about ⁇ 5 to about 10° C.
  • the in situ formed anhydride is adjusted to the desired second contact temperature of about 10 to about 70° C. In another embodiment, the second contact temperature is from about 15 to about 25° C.
  • cellulose is added to the anhydride solution.
  • the anhydride solution can be added to cellulose.
  • the catalyst is added.
  • the catalyst is any acid capable of promoting esterification of cellulose. Examples of such catalysts include, but are not limited to, H 2 SO 4 , HBr, HCl, HClO 4 , or mixtures thereof.
  • the catalyst is H 2 SO 4 .
  • the amount of catalyst that is added is from about 0.25 to about 15 wt % based on weight of cellulose. In another embodiment, the amount of catalyst is from about 2.5 to about 7.5 wt %.
  • the slurry of cellulose is maintained at the second contact temperature for the contact time.
  • the contact time is from about 10 to about 60 min. In another embodiment, the contact time is from about 20 to about 40 min.
  • a second C 2 -C 12 anhydride or mixture of C 2 -C 12 anhydrides is added.
  • the anhydrides or mixtures thereof are C 2 -C 4 anhydrides.
  • the anhydrides are acetic, propionic, butyric, isobutyric anhydride or mixtures thereof.
  • the cellulose containing solution is adjusted to the third contact temperature.
  • the third contact temperature is from about 30 to about 95° C.
  • the third contact temperature is from about 40 to about 60° C.
  • the cellulose containing solution is maintained at the third contact temperature until a cellulose triester with the desired molecular weight is obtained.
  • the second contact time is from about 0.1 to about 24 h.
  • the second contact time is from about 2 to about 8 h.
  • the weight-average molecular weight is from about 5,000 to about 600,000 g/mol.
  • the molecular weight is from about 25,000 to about 250,000 g/mol.
  • the molecular weight is from about 50,000 to about 150,000 g/mol.
  • the catalyst can be neutralized with an appropriate base and isolated by addition of a nonsolvent.
  • suitable bases include, but are not limited to, NaOH, KOH, MgCO 3 , Mg(OAc) 2 , CaCO 3 , Ca(OAc) 2 , Na 2 CO 3 , K 2 CO 3 , NaHCO 3 , or mixtures thereof.
  • nonsolvents include, but are not limited to, H 2 O, MeOH, EtOH, n-PrOH, i-PrOH, i-BuOH, or mixtures thereof. Filtration and drying by methods known to those skilled in the art provides a cellulose triester.
  • the formate substitutent is preferably attached to the C6 hydroxyl of cellulose.
  • the total formate DS is from about 0.7 to about 1.3. In a further embodiment, the total formate DS is from about 0.9 to about 1.1.
  • the formate RDS at C6 is at least 0.4. In yet another embodiment, the formate RDS is at least 0.6.
  • the formate ester can be selectively removed by contacting the fully substituted cellulose formate ester with H 2 O or an alcohol at a preferred contact temperature and time.
  • the alcohol is methanol. It is preferred, but not necessary, to neutralize the catalyst prior to hydrolysis or alcoholysis.
  • the amount of H 2 O or alcohol is from about 5 to about 35 wt %. In another embodiment, the amount of H 2 O or alcohol is from about 10 to about 25 wt %.
  • the contact temperature is from about 25 to about 95° C. In another embodiment, the contact temperature is from about 40 to about 60° C.
  • the contact time is from about 4 to about 36 h. In yet a further embodiment, the contact time is from about 8 to about 24 h.
  • the level of formate ester in the secondary ester can be controlled by selection of the appropriate contact time and temperature.
  • the secondary regiospecific substituted cellulose ester can be isolated in the same manner as the cellulose triester. In general, the RDS of the secondary ester will reflect that established at the triester stage.
  • the polysaccharide esters that can be oxidized in the present invention are those that are soluble in a mixture of carboxylic acid and H 2 O and which have primary hydroxyls available for oxidation.
  • examples of such polysaccharide esters include starch esters and other polysaccharides esters having ⁇ -1,4 glycosidic linkages, pullulan esters and other polysaccharides esters having ⁇ -1,3 glycosidic linkages, cellulose esters and other polysaccharides esters having ⁇ -1,4 glycosidic linkages, and other ⁇ -glucan esters such as those from chitin, chitosan, fructans, glactomannans, glucomannas, xyloglucans, arabinoxylans and the like.
  • the most preferred polysaccharide esters are C 2 -C 10 cellulose esters having primary hydroxyls available for oxidation.
  • a method for converting a primary alcohol to a formyl, carboxylate, or mixture thereof comprising: adding a 4-substituted piperidine nitroxyl derivative wherein the substitutent is capable of hydrogen bonding, a primary oxidant and a terminal oxidant to a mixture to form a reaction mixture, wherein the mixture has a pH of less than about 4 and comprises a compound comprising a primary alcohol functional group; passing of a reaction period sufficient to effect conversion of the primary alcohol functional group, wherein the primary alcohol group is found on the above listing of polysaccharide esters.
  • the primary oxidant is a Mn (III) salt.
  • the reaction media for oxidation is a mixture of carboxylic acid and H 2 O.
  • the carboxylic acids are C 2 -C 10 aliphatic carboxylic acids or mixtures thereof.
  • the carboxylic acids are those, which correspond to the acyl groups attached to the polysaccharide ester.
  • the carboxylic acid in the oxidation of cellulose propionate may be propionic acid and the carboxylic acid mixture in the oxidation of cellulose acetate propionate may be a mixture of propionic acid and acetic acid.
  • the amount of water in the carboxylic acid is from about 1 to about 60 wt % based on total weight of liquids. In another embodiment, the amount of water in the carboxylic acid is from about 5 to about 30 wt %.
  • the catalyst or mediator for oxidation of polysaccharide esters are organic nitroxyl compounds lacking ⁇ -hydrogen atoms.
  • the organic nitroxyl compounds are those arising from the piperidine or pyrrolidine series.
  • the organic nitroxyl compounds are those that can be derived from 4-oxo-2,2,6,6-tetramethylpiperdine.
  • the most preferred organic nitroxyl compound is 2,2,6,6-tetramethylpiperdine-N-oxyl (TEMPO).
  • the preference for TEMPO in preparing cationic C 2 -C 10 oxidized cellulose esters arises from the fact that, when used in combination with appropriate primary oxidants, the oxidation provides a high aldehyde to carboxylate ratio. A high concentration of aldehyde functionality is necessary for subsequent conversion to the cationic functionality (vide infra).
  • the organic nitroxyl compounds are 4-hydroxy-2,2,6,6-tetramethylpiperdine-N-oxyl and derivatives thereof as well as 4-amino-2,2,6,6-tetramethylpiperdine-N-oxyl and derivatives thereof.
  • the most preferred organic nitroxyl compound for the preparation of anionic or zwitterionic C 2 -C 10 oxidized cellulose esters is 4-acetamido-2,2,6,6-tetramethylpiperdine-N-oxyl (NHAcTEMPO).
  • NHAcTEMPO 4-acetamido-2,2,6,6-tetramethylpiperdine-N-oxyl
  • the amount of organic nitroxyl compound is from about 0.0001 to about 0.1 molar equivalents per mole of polysaccharide ester monomer.
  • the amount of organic nitroxyl compound is from about 0.0025 to about 0.075 molar equivalents per mole of polysaccharide ester monomer.
  • the amount organic nitroxyl compound is that amount that will give the desired degree of oxidation under the selected reaction conditions. As such, a broad range of organic nitroxyl compound is contemplated.
  • the preferred primary oxidants are oxidizing agents capable of oxidizing hydroxyamines that arise from the reduction of organic nitroxyls.
  • primary oxidants include, but are not limited to halide salts such as KCl, KBr, NaCl, NaBr, NaI and the like, hypohalites such as NaOCl, NaOBr and the like, metals such as Fe(III), Mn (II), Mn(III), Cu(II) and the like, and mixtures thereof.
  • the primary oxidants include KMnO 4 , Mn(OAc) 3 , Mn 2 O 3 , MnO 2 , Mn(NO 3 ) 2 , MgCl 2 , Mg(OAc) 2 , Cu(NO 3 ) 2 , KCl, KBr, NaBr, NaCl, and NaOCl.
  • the primary oxidants include Mn(NO 3 ) 2 , Cu(NO 3 ) 2 , or mixture thereof
  • the primary oxidant is a 1/1 mixture of Mn(NO 3 ) 2 and Cu(NO 3 ) 2 .
  • the amount of primary oxidant is from about 0.0001 to about 0.1 molar equivalents per mole of polysaccharide ester monomer.
  • the primary oxidant is from about 0.001 to about 0.075 molar equivalents per mole of polysaccharide ester monomer.
  • the amount of primary oxidant is that amount that will give the desired degree of oxidation under the selected reaction conditions. As such, a broad range of primary oxidant is contemplated.
  • the terminal oxidants are any oxidizing agents capable of directly oxidizing hydroxyamines that arise from the reduction of organic nitroxyls or reoxidizing primary oxidants that in turn oxidize the hydroxyamines that arise from the reduction of organic nitroxyls.
  • Examples of terminal oxidants include, but are not limited to, oxygen, ozone, hypohalites such as NaOCl and the like, peroxides such as hydrogen peroxide and the like, peracids such as peracetic acid and the like, and mixtures thereof.
  • the terminal oxidants include oxygen, NaOCl, peracetic acid, and hydrogen peroxide in aqueous carboxylic acid.
  • the amount of terminal oxidant is from about 0.1 to about 10 molar equivalents per mole of polysaccharide ester monomer. In a further embodiment, the amount of primary oxidant is from about 2 to about 5 molar equivalents per mole of polysaccharide ester monomer. In yet a further embodiment, the amount of terminal oxidant is that amount that will give the desired degree of oxidation under the selected reaction conditions. As such, a broad range of terminal oxidant is contemplated.
  • the contact temperature in the oxidation is from about 25 to about 80° C. In another embodiment, the contact temperature is from about 50 to about 60° C. In another embodiment, the contact time is from about 0.1 to about 36 h. In a further embodiment, the contact time is from about 3 to about 12 h. In yet a further embodiment, the contact time is equal to or slightly greater (about 0.01 to about 1 h) than the time that is required to add the terminal oxidant.
  • the addition time of terminal oxidant is from about 0.1 to about 35 h. In another embodiment, the terminal oxidant addition time is from about 2 to about 11 h.
  • the contact pH can range from about 0.1 to about 4. The precise value will be determined by the pH of the carboxylic acid and if the acid used in the esterification or hydrolysis of the polysaccharide ester was neutralized prior to the oxidation. In another embodiment, the contact pH is less than about 2.0. Although it is possible to control pH, it should be understood that in this invention, it is preferred that the pH not be controlled to a particular value during the reaction but that the pH should be allowed to drift during the reaction.
  • Oxidized cellulose esters can be isolated by a number of techniques such as precipitation in a nonsolvent, by spray drying, by spinning of fibers, etc.
  • the method is by precipitation into nonsolvents such as H 2 O, H 2 O/C 2 -C 4 carboxylic acid mixtures, C 1 -C 4 alcohols, C 1 -C 4 esters of acetate or propionate, and the like.
  • the solvent used depends upon the degree of oxidation, the molecular weight of the oxidized polysaccharide, and the number of carbons in the acyl substitutents.
  • the preferred nonsolvents are C 2 -C 4 alcohols such as isopropyl alcohol or n-butanol.
  • the preferred nonsolvent is H 2 O containing from about 5 wt % to about 25 wt % of a C 1 to C 4 carboxylic acid.
  • Acid number is defined as the mg of base (KOH) required to neutralize 1 g of oxidized cellulose ester.
  • KOH base
  • the acid number of the oxidized cellulose ester will be set by the intended end use application and hence a very broad acid number is anticipated.
  • the acid number is greater than 10.
  • the acid number is greater than 30.
  • the acid number is greater than 30 and less than 150.
  • the acid number is greater than 30 and less than 130.
  • the acid number is greater than 30 and less than 90.
  • the acyl DS value will also depend upon the technique that is used to measure the DS.
  • Proton NMR is a common and preferred technique for measuring the acyl DS of cellulose esters. This method relies on determining the amount of glucose monomer by integration of the backbone region of the cellulose ester, which is then divided by 7, which is the number of protons normally attached to the glucose monomer. However, oxidation of the glucose monomer will reduce the number of protons depending upon the extent of oxidation.
  • acyl DS that will increase linearly with oxidation. If hydrolysis of the acyl substitutents is occurring, the increase in DS will not be linear.
  • proton NMR can provide an indication of oxidation for a particular sample.
  • the acyl DS that is obtained by proton NMR for the oxidized cellulose ester is referred to as the apparent acyl DS.
  • the apparent acyl DS of the oxidized cellulose esters is a crucial property for virtually all applications and the preferred apparent acyl DS will vary depending upon the intended application. In one embodiment of this invention, the apparent acyl DS will be at least 0.6. In a further embodiment, the apparent acyl DS is from about 1.5 to about 3.1. In a further embodiment, the apparent acyl DS is from about 1.7 to about 2.8.
  • the molecular weight of the oxidized cellulose esters is another important property for most applications and the preferred molecular weight will vary depending upon the intended application.
  • molecular weight by selection of the acyl group attached to the cellulose polymer and by control of the amount of aldehyde and hydroxyl functional groups in the final product through selection of appropriate reaction conditions, it is possible to have molecular weights in the oxidized cellulose ester that are less than or greater than that of the cellulose ester used in the oxidation.
  • the increase in molecular weight above that of the starting molecular weight of the cellulose esters is thought to be due to small concentrations of aldehyde functional groups that lead to effective cross-linking of the oxidized cellulose ester by formation of acetal or hemiacetal linkages.
  • the weight-average molecular weight is at least 5,000 g/mol.
  • the range for molecular weight is from about 10,000 to about 900,000 g/mol. In a further embodiment, the range is from about 20,000 to about 400,000 g/mol.
  • the ratio of carboxylate to aldehyde can be used to adjust the measured molecular weight of the oxidized cellulose ester. This ratio can also be used to gain entry into a number of unique oxidized cellulose ester derivatives.
  • the ratio of carboxylate to aldehyde can be adjusted through selection of appropriate reaction conditions.
  • the reaction parameters which can impact this ratio, include water concentration in the reaction media, type and concentration of organic nitroxyl compound, type and concentration of primary and terminal oxidant, reaction temperature and time, and the type of cellulose ester being oxidized.
  • the disclosure of this invention is sufficient to teach one of ordinary skill in the art how to arrive at a particular carboxylate to aldehyde ratio.
  • the ratio of carboxylate to aldehyde will be at least 5:1.
  • the carboxylate to aldehyde range is from about 6:1 to about 100:1.
  • the range is when the carboxylate to aldehyde range is from about 10:1 to about 50:1. In some cases, it may be desirable that that there be no aldehyde.
  • the ratio of carboxylate to aldehyde will be less than 1:5. In some cases, it is preferred that there be no carboxylate. In one embodiment, the carboxylate to aldehyde range is from about 1:6 to about 1:100. In another embodiment, the carboxylate to free aldehyde range is from about 1:10 to about 1:50.
  • the cellulose ester interpolymer has a degree of polymerization of at least 10. In another embodiment, the cellulose ester interpolymer has a degree of polymerization of at least 25. In a further embodiment, the cellulose ester interpolymer has a degree of polymerization of between 25 and 50. In yet another embodiment, the cellulose ester interpolymer has a degree of polymerization of at least 250.
  • the ratio of carboxylate to aldehyde be from about 5:1 to about 1:5.
  • a more preferred range is when the carboxylate to aldehyde range is from about 4:1 to about 1:4.
  • An even more preferred range is from about 2:1 to about 1:2.
  • the aldehyde functionality is converted to cationic functionality.
  • the conversion of the aldehyde functionality can occur during the oxidation or immediately after oxidation but before isolation of the oxidized product.
  • the cationic or zwitterionic oxidized cellulose ester precursor can be isolated and converted to the cationic or zwitterionic oxidized cellulose ester in post reactions. In the case of isolation of the oxidized cellulose ester prior to conversion to the cationic or zwitterionic oxidized cellulose ester, it is preferred that the oxidized cellulose ester not be dried prior to the reductive amination step.
  • the oxidized cellulose ester may be precipitated in a non-solvent such as methanol.
  • a non-solvent such as methanol.
  • the oxidized cellulose is then stored methanol wet until ready for use.
  • the methanol can be removed by dissolving the oxidized cellulose ester in the reaction reagents, e.g. acetic acid and benzyl amine, and bubbling air or N 2 through the solution to remove the methanol. Because fewer acetal linkages are formed relative to drying the oxidized cellulose ester, this process allows the oxidized cellulose to be more easily dissolved in the reaction solvents.
  • the aldehyde functionality can be converted to a cationic functionality by treating the aldehyde with a source of NH 3 or a primary amine in the presence of hydrogen and a hydrogenation catalyst (reductive amination).
  • the source of NH 3 is ammonia gas or other sources such as NH 3 Cl.
  • the preferred amines are primary amines having from 1 to 14 carbon atoms. Examples of amines include, but are not limited to, ethylamine, propylamine, butylamine, benzylamine, or mixture thereof.
  • the hydrogenation catalyst is Pd supported on inert substances such as carbon. Other reducing agents can also be utilized such as sodium cyanoborohydride, sodium borohydride, or amine salts of formic acid.
  • the amount of amine present in the cationic or zwitterionic oxidized cellulose ester can be determined by a variety of methods such as by titration methods similar to that used to determine acid number or by other methods such as proton NMR.
  • the quantity of amine in the cationic or zwitterionic oxidized cellulose ester is preferably determined by proton NMR when possible.
  • the DS of amine is referred to as the apparent amine DS for the same reasons described above.
  • the apparent amine DS is at least about 0.05.
  • the apparent amine DS is about 0.2 to about 0.7.
  • Another aspect of the present invention is oxidation of polysaccharides with available primary hydroxyls in a mixture of carboxylic acid and H 2 O.
  • polysaccharides examples include starch and other polysaccharides having ⁇ -1,4 glycosidic linkages, pullulan and other polysaccharides having ⁇ -1,3 glycosidic linkages, cellulose and other polysaccharides having ⁇ -1,4 glycosidic linkages, and other ⁇ -glucans such as those from chitin, chitosan, fructans, glactomannans, glucomannas, xyloglucans, arabinoxylans and the like.
  • the most preferred polysaccharide is cellulose.
  • the limitations noted above for polysaccharide esters are also applicable to the oxidation of polysaccharides.
  • the pH during the oxidation be less than about 4 and, in another embodiment, less than about 2.
  • no prior treatment of the cellulose is necessary as the reaction media for oxidation of cellulose by the methods of the present invention is sufficient to disrupt the crystallinity of the native cellulose.
  • the cellulose oxidized by the methods of the present invention has an acid number of at least 10.
  • the oxidized cellulose has an acid number of at least 30. It is also preferred that the oxidized cellulose prepared by the methods of the present invention have little solubility in water.
  • the product is characterized by having only a small or no water-soluble fractions.
  • the methods of the present invention are compatible with the methods commonly utilized in the esterification of cellulose. That is, after filtering to remove the liquids, the oxidized cellulose can be esterified by methods well known to those skilled in the art.
  • the cellulose ester interpolymers of the present invention and other compositions disclosed herein may be useful in a number of different types of applications, for example, the cellulose ester interpolymers wherein the C2 and C3 positions of each of the anhydroglucose units of the cellulose ester interpolymer are in the alcohol oxidation state, and comprising anhydroglucose units
  • R 1 , R 2 , R 3 , R 4 , and R 5 are independently selected from the group consisting of hydrogen and C 2 -C 12 acyl groups, wherein at least one of R 1 , R 2 , R 3 , R 4 , and R 5 is a C 2 -C 12 acyl group; and X is formyl, hydroxymethylene, aminomethyl, R 6 —NH—CH 2 — or carboxy or a mixture thereof, wherein R 6 is selected from the group consisting of alkyl, aryl, or alkylene-aryl, provided when at least some of X is carboxy, the acid number is greater than 10; wherein the anhydroglucose units A and B comprise greater than 65% of the total anhydroglucose units of the cellulose portion of the cellulose ester interpolymer.
  • cellulose ester interpolymers may be useful in a variety of coating compositions such as enteric coatings for medicaments, architectural coatings, maintenance coatings, industrial coatings, automotive coatings, textile coatings, inks, adhesives, and coatings for metal, paper, wood, and plastics, as binder resins.
  • the cellulose ester interpolymers may be particularly useful in waterborne coating applications containing pigments.
  • oxidized cellulose esters of the present invention may be useful in drug delivery compositions, as an antiviral agent, as a compatibilizer in thermoplastic compositions, and in personal care compositions.
  • this invention relates to coating compositions comprising oxidized cellulose esters of the present invention.
  • the oxidized cellulose esters of the invention may be incorporated into coating compositions in the same manner as known cellulose esters and are used with the conventional components and or additives of such compositions.
  • the coating compositions may be clear or pigmented.
  • Coating compositions containing carboxylated cellulose ether esters are known in the art and are described, for example, in U.S. Pat. No. 5,668,273, incorporated herein by reference.
  • coating compositions utilizing the cellulose ester interpolymers of the invention; in one embodiment, the cellulose ester interpolymers wherein the C2 and C3 positions of each of the anhydroglucose units of the cellulose ester interpolymer are in the alcohol oxidation state, and comprising anhydroglucose units
  • R 1 , R 2 , R 3 , R 4 , and R 5 are independently selected from the group consisting of hydrogen and C 2 -C 12 acyl groups, wherein at least one of R 1 , R 2 , R 3 , R 4 , and R 5 is a C 2 -C 12 acyl group; and, X is formyl, aminomethyl, R 6 —NH—CH 2 — or carboxy or a mixture thereof, wherein R 6 is selected from the group consisting of alkyl, aryl, or alkylene-aryl, provided when at least some of X is carboxy, the acid number is greater than 10; wherein the anhydroglucose units A and B comprise greater than 65% of the total anhydroglucose units of the cellulose portion of the cellulose ester interpolymer.
  • the invention provides a coating composition comprising
  • the cellulose esters interpolymers are anionic C 2 -C 8 cellulose esters having an acid number from about 10 to about 200.
  • the oxidized cellulose esters are anionic C 2 -C 4 cellulose esters having an acid number from about 30 to about 80.
  • the concentration of oxidized cellulose esters is typically from about 0.1 to about 50 wt % based on total weight of oxidized cellulose ester and added resin. In another embodiment, the concentration of oxidized cellulose ester is from about 3 to about 30 wt %.
  • the cellulose ester interpolymers may be compatible with a wide range of resinous materials such as those used in coating and ink compositions.
  • Classes of resins with which the carboxylated cellulose esters are compatible include, but are not limited to, polyesters, polyester-amides, cellulose esters, alkyds, polyurethanes, epoxy resins, polyamides, acrylics, vinyl polymers, polyisocyanates, melamines, silicone resins, and nitrocellulose.
  • the concentration of the cellulose ester interpolymer in the coating composition is from about 0.1 to about 50 wt % based on total weight of oxidized cellulose ester and resin. In another embodiment, the concentration of cellulose ester interpolymer is from about 5 to about 30 wt %.
  • the cellulose ester interpolymers of the present invention are compatible with a number of solvents.
  • solvents include, but are not limited to methanol; ethanol; methylene chloride; diacetone alcohol; lower alkanoic acids, such as formic acid, acetic acid, and propionic acid; lower alkyl ketones, such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, and methyl n-amyl ketone; esters, such as methyl acetate, ethyl acetate, isopropyl acetate, n-propyl acetate, n-butyl acetate, 2-ethylhexyl acetate, isobutyl acetate, 2-butoxy-ethyl acetate, 1-methoxy-2-propyl acetate, 2-ethoxy-ethyl acetate, ethyl-3-ethoxypropionat
  • the concentration of solvent in the coating compositions containing the cellulose ester is typically from about 30 to about 95 wt % based on the total weight of oxidized cellulose ester, resin, and solvent.
  • concentration of solvent in the coating compositions containing the cellulose ester is typically from about 30 to about 95 wt % based on the total weight of oxidized cellulose ester, resin, and solvent.
  • selection of the compatible solvent will depend upon a number of factors including DS of the oxidized cellulose ester, the type of substitutent, the degree of oxidation, the molecular weight, and the like.
  • a coating formulation containing the cellulose esters interpolymers of the present invention may be applied to a variety of surfaces, substrates, or articles, e.g., paper; plastic; metal such as steel and aluminum; wood; gypsum board; concrete; brick; masonry; or galvanized sheeting.
  • the type of surface, substrate, or article to be coated generally determines the type of coating formulation used.
  • the coating formulation may be applied using means known in the art. For example, a coating formulation may be applied by spraying, brushing, rolling or any other application method to coat a substrate.
  • the cellulose esters interpolymers of the invention are also useful as a major film-forming component in both curing and non-curing finishes of wood coatings. Accordingly, the invention also relates to curing type wood finishes comprising from about 5 to about 20 wt % an oxidized cellulose ester of the present invention, about 15 to about 25 wt % of an alkyd resin, about 2 to about 5 percent by weight of a melamine resin, or up to about 5 to about 10 percent by weight of a urea formaldehyde resin, a relatively small amount of a silicone resin and a solvent system comprising suitable solvents such as xylene, toluene, ethanol, n-butyl alcohol, and methyl ethyl ketone.
  • Flatting agents such as SYLOID 83 and SYLOID 378 available from W.R. Grace, may also be employed.
  • the cellulose esters interpolymers of the present invention can be formulated into ink formulations.
  • the oxidized cellulose ester functions as a medium to disperse the pigments for the ink and also serve as a major film-forming resin.
  • another embodiment of the invention relates to ink compositions comprising from about 30 to about 70% by weight of a oxidized cellulose ester, from about 30 to about 70% by weight of an ink pigment and a solvent present in an amount effective to provide a viscosity suitable for applying the ink composition under the desired conditions.
  • Ink compositions of the invention may also contain common ink additives depending on need of a particular ink or printing method.
  • ink additives include, but are not limited to wetting agents, leveling agents, rheology additives, additives to promote resolubility/rewet on the press, coalescing aids, pigment wetting agents, dispersing agents, surfactants, waxes, defoaming agents, antifoaming agents, and modifying polymers or co-resins.
  • concentration of the pigment depends upon the particular pigment employed and the color and degree of hiding desired in the ink composition.
  • Pigments which are useful in the ink compositions of the invention, are those well known in the art and are described, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, 2d Ed., Vol. 11, pp. 613-615.
  • the solvents useful in the ink compositions of the invention are also well known in the art and are described, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, 2d Ed., Vol. 11, pp. 621-623.
  • Preferred solvents include ethanol, ethyl acetate, isopropanol, diacetone alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and mixtures thereof.
  • Cellulose esters interpolymers of the present invention are particularly useful as a pigment dispersing agent.
  • Non-oxidized cellulose esters have found utility in pigment dispersions by blending the cellulose ester and a pigment with heat and/or shear to disperse the pigment. In this manner, pigments can be dispersed in coating formulations, thereby providing high coloring power and good transparency while using a minimal amount of pigment.
  • Such pigment dispersions can be improved by the use of the oxidized cellulose esters of the present invention in place of conventional cellulose esters. We have found that the oxidized cellulose esters of the present invention impart markedly improved wetting properties to the pigment dispersion.
  • Mixtures of oxidized cellulose esters and pigments at weight ratios of about 20:80 to 50:50 may be prepared. These dispersions can be prepared on a two-roll mill or in a ball mill, Kady mill, sand mill, and the like.
  • the invention provides a pigment dispersion comprising about 40 to 90 weight percent by weight of at least one pigment and correspondingly about 10 to 60 weight percent of cellulose ester interpolymers wherein the C2 and C3 positions of each of the anhydroglucose units of the cellulose ester interpolyer are in the alcohol oxidation state, and comprising anhydroglucose units
  • the oxidized cellulose esters and pigment dispersions can be formulated into either lacquer or enamel type coatings where they are expected to be useful as rheology modifiers and/or binder components providing improved aluminum flake orientation and improved hardness. They can be applied to a substrate in the form of an organic solvent solution, an amine neutralized waterborne dispersion, a fully neutralized aqueous/organic colloidal dispersion, or as a zero VOC dispersion in aqueous ammonia. It is further expected that they will provide a water clear, high gloss, protective coating for a variety of substrates, especially metal and wood.
  • the cellulose ester interpolymers of the present invention can be relatively hard polymers and have high glass transition temperatures. They can be added to other resins to improve the coating hardness and to improve properties such as slip, sag resistance, mar resistance, flow, leveling, and dry time.
  • cross linkers such as melamines or isocyanates may be added to react with the hydroxyl containing oxidized cellulose esters or with other resins.
  • the preferred melamine cross-linking agents include hexamethoxymethylamine, tetramethoxymethylbenzo-guanamine, tetramethoxymethylurea, mixed butoxy/methoxy substituted melamines, and the like.
  • Typical isocyanate cross linking agents and resin include hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), and toluene diisocyanate.
  • carboxyl functional resins e.g., epoxy resins or glycidyl-functional resins.
  • Preferred epoxy functional resins generally have a molecular weight of about 300 to about 4000, and have approximately 0.05 to about 0.99, epoxy groups per 100 g of resin (i.e., 100-2000 weight per epoxy (WPE)).
  • WPE weight per epoxy
  • Such resins are widely known and are commercially-available under the EPON trademark of the Shell Chemical Company, the ARALDITE trademark of CIBA-Geigy, and D.E.R. resins of the Dow Chemical Company.
  • the cellulose ester interpolymers of the present invention are particularly useful in waterborne coating compositions.
  • the preferred cellulose ester interpolymers are anionic C 2 -C 8 cellulose esters having an acid number from about 10 to about 200.
  • the most preferred cellulose ester interpolymers are anionic C 2 -C 4 cellulose esters having an acid number from about 30 to about 80.
  • the cellulose ester interpolymers of this invention may be dissolved in organic solvents, partially neutralized, and dispersed in water.
  • organic solvents include but are not limited to 2-butanone, methyl amyl ketone, methanol, ethanol, ethyl 3-ethoxypropionate, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether and the like.
  • Dispersion of the modified cellulose ester of the present invention in water requires about 10 to about 100% neutralization of the pendant carboxylate groups with an amine.
  • Typical amines include but are not limited to ammonia, piperidine, 4-ethylmorpholine, diethanolamine, triethanolamine, ethanolamine, tributylamine, dibutylamine, and dimethylamino ethanol.
  • the concentration of the resin in the coating composition is from about 0.1 to about 50 wt % based on total weight of oxidized cellulose ester and resin. More preferred is when the concentration of resin is from about 5 to about 30 wt %.
  • the concentration of cellulose ester interpolymers is typically from about 0.1 to about 50 wt % based on total weight of oxidized cellulose ester and added resin. More preferred is when the concentration of oxidized cellulose ester is from about 0.5 to about 30 wt %.
  • the weight of resin and oxidized cellulose ester in the total composition is from about 5 to about 70 wt %.
  • the weight of resin and oxidized cellulose ester in the total composition is from about 10 to about 50 wt %.
  • the organic solvent preferably comprises from about 0 to about 20 wt % of the total composition. More preferred is when the organic solvent preferably comprises from about 5 to about 15 wt % of the total composition.
  • the invention provides a waterborne coating composition
  • a waterborne coating composition comprising
  • the above compositions are further comprised of one or more coatings additives.
  • coatings additives are generally present in a range of about 0.1 to 15 weight percent, based on the total weight of the composition.
  • coatings additives include leveling, rheology, and flow control agents such as silicones, fluorocarbons or cellulosics; flatting agents; pigment wetting and dispersing agents; surfactants; ultraviolet (UV) absorbers; UV light stabilizers; tinting pigments; defoaming and antifoaming agents; anti-settling, anti-sag and bodying agents; anti-skinning agents; anti-flooding and anti-floating agents; fungicides and mildewcides; corrosion inhibitors; thickening agents; or coalescing agents.
  • flatting agents examples include synthetic silica, available from the Davison Chemical Division of W. R. Grace & Company under the trademark SYLOID; polypropylene, available from Hercules Inc., under the trademark HERCOFLAT; synthetic silicate, available from J. M Huber Corporation under the trademark ZEOLEX.
  • dispersing agents and surfactants include sodium bis(tridecyl) sulfosuccinnate, di(2-ethyl hexyl) sodium sulfosuccinnate, sodium dihexylsulfosuccinnate, sodium dicyclohexyl sulfosuccinnate, diamyl sodium sulfosuccinnate, sodium diisobutyl sulfosuccinate, disodium iso-decyl sulfosuccinnate, disodium ethoxylated alcohol half ester of sulfosuccinnic acid, disodium alkyl amido polyethoxy sulfosuccinnate, tetrasodium N-(1,2-dicarboxy-ethyl)-N-oxtadecyl sulfosuccinnamate, disodium N-octasulfosuccinnamate, sulfated ethoxylated nonyl
  • viscosity, suspension, and flow control agents examples include polyaminoamide phosphate, high molecular weight carboxylic acid salts of polyamine amides, and alkyl amine salt of an unsaturated fatty acid, all available from BYK Chemie U.S.A. under the trademark ANTI TERRA.
  • Further examples include polysiloxane copolymers, polyacrylate solution, cellulose esters, hydroxyethyl cellulose, hydrophobically-modified hydroxyethyl cellulose, hydroxypropyl cellulose, polyamide wax, polyolefin wax, carboxymethyl cellulose, ammonium polyacrylate, sodium polyacrylate, and polyethylene oxide.
  • fungicides examples include 4,4-dimethyloxazolidine, 3,4,4-trimethyl-oxazolidine, modified barium metaborate, potassium N-hydroxy-methyl-N-methyldithiocarbamate, 2-(thiocyano-methylthio) benzothiazole, potassium dimethyl dithiocarbamate, adamantane, N-(trichloromethylthio) phthalimide, 2,4,5,6-tetrachloroisophthalonitrile, orthophenyl phenol, 2,4,5-trichlorophenol, dehydroacetic acid, copper naphthenate, copper octonate, organic arsenic, tributyl tin oxide, zinc naphthenate, and copper 8-quinolinate.
  • U.V. absorbers and U.V. light stabilizers include substituted benzophenone, substituted benzotriazole, hindered amine, and hindered benzoate, available from American Cyanamide Company under the trade name Cyasorb UV, and available from Ciba Geigy under the trademark TINUVIN, and diethyl-3-acetyl-4-hydroxy-benzyl-phosphonate, 4-dodecyloxy-2-hydroxy benzophenone, and resorcinol monobenzoate.
  • Pigments suitable for use in the coating compositions envisioned by the present invention are the typical organic and inorganic pigments, well-known to one of ordinary skill in the art of surface coatings, especially those set forth by the Colour Index, 3d Ed., 2d Rev., 1982, published by the Society of Dyers and Colourists in association with the American Association of Textile Chemists and Colorists. Examples include, but are not limited to the following: CI Pigment White 6 (titanium dioxide); CI Pigment Red 101 (red iron oxide); CI Pigment Yellow 42, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4 (copper phthalocyanines); CI Pigment Red 49:1; and CI Pigment Red 57:1.
  • This invention also relates to oral drug delivery compositions comprising the cellulose ester interpolymers of the present invention.
  • the cellulose ester interpolymers are used as an enteric coating for a solid core containing the therapeutic agent.
  • the cellulose ester interpolymers are used as a component in a blend used as an enteric coating.
  • the cellulose ester interpolymers are used as release rate modifiers or solubility modifiers of therapeutic agents from a solid core.
  • physical mixtures of cellulose ester interpolymers and solubility modifiers are used for the controlled release of therapeutic agents from a solid core.
  • vesicles of cellulose ester interpolymers containing therapeutic agents acts as release rate and solubility modifiers in the controlled release of therapeutic agents from a solid core.
  • the cellulose ester interpolymers are bioadhesive components in a solid core and act to increase the bioabsorption of therapeutic agents.
  • the cellulose ester interpolymers are anionic, cationic, or zwitterionic C 2 -C 12 cellulose esters.
  • the preferred cellulose ester interpolymers will be determined by the mode selected for delivery of the therapeutic agent from the oral formulation.
  • the invention provides an oral pharmaceutical composition
  • a composition comprising one or more therapeutic agents having coated thereon or admixed therewith a composition comprising one or more cellulose ester interpolymers wherein the C2 and C3 positions of each of the anhydroglucose units of the cellulose ester interpolyer are in the alcohol oxidation state, and comprising anhydroglucose units
  • the cellulose ester interpolymers are used as enteric coatings of a solid core containing at least one therapeutic agent
  • the cellulose ester interpolymers are anionic C 2 -C 4 cellulose esters having an acid number from about 30 to about 120.
  • the cellulose ester interpolymers are anionic C 2 cellulose esters having an acid number from about 40 to about 100.
  • the enteric coating can be comprised of a single preferred oxidized cellulose ester or a mixture of cellulose ester interpolymers.
  • the cellulose ester interpolymers represent one or more components of the blend
  • the cellulose ester interpolymers are anionic C 2 -C 4 cellulose esters having an acid number from about 30 to about 120.
  • the cellulose ester interpolymers are anionic C 2 cellulose esters having an acid number from about 40 to about 100.
  • the other components of the blend can be one or more of any water soluble, pH sensitive, or water insoluble polymer useful in enteric coatings. Examples of useful water soluble polymers include, but are not limited to, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, or methyl cellulose.
  • pH sensitive polymers include, but are not limited to, cellulose acetate phthalate, cellulose acetate succinate, cellulose acetate trimellitate, or hydroxypropyl methyl cellulose phthalate.
  • useful water insoluble polymers include, but are not limited to, cellulose acetate, cellulose acetate propionate, or cellulose acetate butyrate.
  • the cellulose ester interpolymers or blends thereof and optional additives are dissolved in a suitable solvent or mixture of solvents.
  • the solid core containing the therapeutic agent can be coated with these cellulose ester interpolymers solutions by a number of processes well known to those skilled in the art such as fluidized bed or side vented pan coating processes.
  • preferred solvents in the present invention include alcohols, ketones, ethers, esters, and chlorinated hydrocarbons.
  • these solvents include, but are not limited to, ethanol, acetone, 2-butanone, 2-pentanone, ethyl acetate, propyl acetate, propyl ether, tetrahydrofuran, methylene chloride, chlorobenze, and the like.
  • these solvents may contain from about 0.01 to about 50 wt % H 2 O.
  • the optional additives include plasticizers, pigments, colorants, stabilizers, antioxidants, and waxes. Commonly used plasticizers include, but are not limited to, diethyl phthalate, dioctyl phthalate, triacetin, polyethylene glycol, and the like.
  • the invention provides a method for treating a mammal in need thereof, with at least one therapeutic agent, which comprises administering to said mammal an oral pharmaceutical composition comprising a therapeutic agent having coated thereon or admixed therewith a composition comprising a cellulose ester interpolymer wherein the C2 and C3 positions of each of the anhydroglucose units of the cellulose ester interpolyer are in the alcohol oxidation state, and comprising anhydroglucose units
  • the preferred cellulose ester interpolymers are anionic, cationic, or zwitterionic C 2 -C 8 cellulose esters.
  • the most preferred cellulose ester interpolymers are anionic C 2 -C 4 cellulose esters having an acid number from about 40 to about 120.
  • the modifier may be a single preferred oxidized cellulose ester or a mixture of cellulose ester interpolymers.
  • the cellulose ester interpolymers can be incorporated into the solid core along with the therapeutic agent by a number of techniques well known to those skilled in the art.
  • the solid core comprises one or more oxidized cellulose ester, a pharmaceutically acceptable carrier, and a therapeutically effective amount of therapeutic agent.
  • a film coating optionally surrounds the solid core.
  • Solid core formulations of the present invention are generally administered with pharmaceutically acceptable carriers or diluents, the proportion and nature of which are determined by the solubility and chemical properties of the therapeutic agents selected, the chosen dosage form, and standard pharmaceutical practice.
  • Solid oral forms may contain conventional excipients, for instance: lactose, sucrose, magnesium stearate, resins and like materials, flavoring, coloring, buffering, preserving, or stabilizing, agents.
  • release rate modifier means cellulose ester interpolymers which serve to modify the rate of release of therapeutic agents.
  • the release rate modifier will assist in providing a controlled release of the therapeutic agent and can cooperate with other components in the formulation to provide a delayed, sustained, timed, pH dependent, targeted, or further controlled delivery of the therapeutic agent.
  • the invention provides a method wherein the cellulose ester interpolymer modifies ordinary release rate profile of the therapeutic agent.
  • the point of the gastrointestinal tract where a given therapeutic agent is absorbed will be modified.
  • solubility enhancers in the solid core along with the cellulose ester interpolymers may serve to provide for the increased solubility and oral bioavaliability of the therapeutic agents.
  • the solubility enhancer can be any agent which will aid in increasing the water solubility of the therapeutic agent.
  • the solubility enhancer can be incorporated with the oxidized cellulose ester release modifier and therapeutic agent as a physical mixture.
  • the solubility enhancer and therapeutic agents can be incorporated into the solid core with the oxidized cellulose ester release modifier as a complex or as vesicles.
  • solubility enhancers include water-soluble cyclodextrins, cyclodextrin derivatives, and polyethyleneoxide-polypropyleneoxide block copolymers.
  • Preferred cyclodextrin derivatives include hydroxybutenyl cyclodextrins (U.S. Pat. No. 6,479,467, incorporated herein by reference) and sulfohydroxybutenyl cyclodextrins (U.S. Pat. No. 6,610,671, incorporated herein by reference).
  • Preferred polyethyleneoxide-polypropyleneoxide block copolymers are available from BASF Corporation under the trade name Pluronics.
  • the pharmaceutical compositions of the present inventions may include water-soluble CD or CD derivatives.
  • the CD or CD derivative is or is derived from a CD of any ring size, including but not limited to ⁇ , ⁇ , or ⁇ -cyclodextrins.
  • the hydroxybutenyl cyclodextrin is hydroxybutenyl- ⁇ , ⁇ , or ⁇ -cyclodextrin.
  • the hydroxybutenyl cyclodextrin derivative is sulfonated hydroxybutenyl- ⁇ , ⁇ , or ⁇ -cyclodextrin.
  • the hydroxybutenyl cyclodextrin is hydroxybutenyl- ⁇ -cyclodextrin and the hydroxybutenyl cyclodextrin derivative is sulfonated hydroxybutenyl- ⁇ -cyclodextrin.
  • the hydroxybutenyl- ⁇ -cyclodextrins have a molar substitution (MS, wherein MS is the total number of substitutents attached to the CD) from about 1 to about 12.
  • MS is the total number of substitutents attached to the CD
  • the hydroxybutenyl- ⁇ -cyclodextrins are hydroxybutenyl- ⁇ -cyclodextrins with a MS from about 3 to about 10.
  • the hydroxybutenyl- ⁇ -cyclodextrins are water-soluble and have a MS from about 4 to about 7.
  • the hydroxybutenyl- ⁇ -cyclodextrins are water-soluble and have a MS from about 4.5 to about 5.5.
  • the hydroxybutenyl- ⁇ -cyclodextrins are water-soluble and have a MS of about 5.
  • the hydroxybutenyl cyclodextrin derivatives are sulfonated hydroxybutenyl- ⁇ , ⁇ , or ⁇ -cyclodextrins.
  • the sulfonated hydroxybutenyl cyclodextrins are sulfonated hydroxybutenyl- ⁇ -cyclodextrins comprising at least one hydroxybutyl sulfonate substitutent.
  • the sulfonated hydroxybutenyl- ⁇ -cyclodextrins have a MS of hydroxybutyl sulfonate from about 0.02 to about 7.
  • the hydroxybutenyl- ⁇ -cyclodextrins have a MS of hydroxybutyl sulfonate from about 0.1 to about 2.
  • MS of hydroxybutyl sulfonate from about 0.1 to about 2.
  • these cyclodextrin ethers contain both hydroxybutenyl substitutents and hydroxybutyl sulfonate substitutents.
  • the total MS is provided by the sum of the hydroxybutenyl MS and the hydroxybutyl sulfonate. In some embodiments, the total MS is from about 0.02 to about 12.
  • cyclodextrin ethers containing at least one hydroxybutyl sulfonate substitutent optionally further comprise additional alkyl, sulfinate, or disulfonate substitutents.
  • the cellulose ester interpolymers may serve as solubility modifiers of one or more therapeutic agents in the solid core.
  • the cellulose ester interpolymers act as solubility modifiers of therapeutic agents
  • the preferred cellulose ester interpolymers are anionic, cationic, or zwitterionic C 2 -C 12 cellulose esters.
  • the more preferred cellulose ester interpolymers are one or more anionic C 2 -C 8 cellulose esters having an acid number from about 40 to about 120.
  • the more preferred cellulose ester interpolymers are one or more anionic C 2 -C 4 cellulose esters having an acid number from about 40 to about 120.
  • the oxidized cellulose ester and the therapeutic agent can be combined in the solid core as a physical mixture.
  • the therapeutic agents and the oxidized cellulose ester can be combined to form blends, microspheres, nanospheres, or hydrogels prior to incorporation into the solid core.
  • the blends can be formed by first dissolving the cellulose ester interpolymers in an appropriate solvent and dissolving the therapeutic agents in the same or second solvent. A blend is then formed by mixing the two solutions followed by removal of the solvents by methods known to those skilled in the art.
  • the microspheres, nanospheres, or hydrogels can be formed by an emulsification-interfacial cross-linking process or by complexation between oppositely charged macromolecules.
  • the complimentary charged macromolecule to the cellulose ester interpolymers may be the complimentary charged cellulose ester interpolymer.
  • an anionic C 2 -C 12 cellulose esters having an acid number from about 40 to about 120 may be complexed with a cationic C 2 -C 12 cellulose esters of the present invention in the presence of a therapeutic agent forming the desired microsphere or nanosphere.
  • a zwitterionic C 2 -C 12 cellulose ester the complexation leading to formation of the desired microsphere or nanosphere may result from internal ionic interactions. It is not necessary that the complimentary charged macromolecule be an oxidized cellulose ester.
  • Examples, but not limited to, of complimentary charged macromolecules for anionic cellulose ester interpolymers are chitosans having from about 40% to about 60% N-acetyl groups and derivatives thereof.
  • Examples, but not limited to, of complimentary charged macromolecules for cationic cellulose ester interpolymers are carboxymethyl cellulose, alginates, xanthan, hyaluronic acid, and derivatives thereof.
  • the microspheres, nanospheres, or hydrogels can be isolated as powders by techniques known to those skilled in the art such as spray frying or freeze drying.
  • solubility modifier means cellulose ester interpolymers which serve to modify the solubility of therapeutic agents which are otherwise poorly water-soluble.
  • the cellulose ester interpolymers may act as both a release rate modifier and as a solubility modifier of therapeutic agents.
  • the invention provides a method for increasing the solubility of the at least one therapeutic agent, thereby increasing its oral bioavailability.
  • the cellulose ester interpolymers incorporated as a solid core component can function as a bioadhesive.
  • a bioadhesive is defined as a material that adheres or interacts strongly with biological surfaces such as mucous membranes or skin tissue. The net effect is to localize the therapeutic agent thereby increasing its bioavaliability.
  • the preferred cellulose ester interpolymers are anionic, cationic, or zwitterionic C 2 -C 12 cellulose esters. More preferred are anionic, cationic, or zwitterionic C 2 -C 8 cellulose esters.
  • therapeutic agent means any bioactive agent capable of eliciting the required or desired therapeutic response from a patient when administered orally or bucally.
  • a patient is any living human or animal.
  • therapeutic agents include antineoplastics, antiviral agents, antidiabetic agents, antidepressants, antifungal agents, antibacterial agents, antimigrane, antiprotozoal agents, antisense agents, androgens, estrogens, sedatives, serotonin antagonists, narcotic antagonists, narcotic agonists, proteins, peptides, steroids, tranquilizers, antipsychotics, antidepressants, antiallergics, antianginals, antiarthritics, antiasthmatics, antidiabetics, antidiarrheal drugs, anticonvulsants, antigout drugs, antihistamines, antipruritics, anticoagulants, emetics, antiemetics, antispasmondics, appetite suppressants, neuroactive substances, neurotransmitter agonist
  • Non-limiting examples of therapeutic agents include orally-active forms of the following: abacavir, acarbose, acebutolol, acetazolamide, acetohexamide, acrivastine, acutretin, acyclovir, alatrofloxacin, albendazole, albuterol, alclofenac, alendronate, allopurinol, aloxiprin, alprazolam, alprenolol, alprostadil, amantadine, amiloride, aminoglutethimide, amiodarone, amitriptyline, amlodipine, amodiaquine, amoxapine, amoxapine, amphetamine, amphotericin, amprenavir, amrinone, amsacrine, amyl nitrate, amylobarbital, amylobarbitone, anastrozole, arzoxifene, aspirin, astemizole,
  • the cellulose ester interpolymers of the present invention may function as a therapeutic agent.
  • the cellulose ester interpolymers may be effective in decreasing or preventing the frequency of transmission of the human immunodeficiency virus, herpes viruses, or sexually transmitted bacterial infections through administration to a human of an anti-human immunodeficiency virus amount or an anti-herpes virus amount or an anti-bacterial amount of the oxidized cellulose ester.
  • the anti-viral or antibacterial oxidized cellulose ester may be used either alone or in combination with a pharmaceutically acceptable carrier or diluent.
  • the ionic charge of the cellulose ester interpolymers of the present invention is covalently attached to the backbone of the polysaccharide via a carbon-carbon bond and is not susceptible to hydrolysis which will render the polysaccharide derivative inactive.
  • the preferred cellulose ester interpolymers are anionic, cationic, or zwitterionic C 2 -C 12 cellulose esters. More preferred cellulose ester interpolymers are anionic C 2 -C 8 cellulose esters having an acid number from about 30 to about 200. The most preferred anionic cellulose esters have an acid number from about 60 to about 150.
  • thermoplastic compatibilizers comprising the cellulose ester interpolymers of the present invention.
  • the oxidized cellulose ester thermoplastic compatibilizer will improve the miscibility between the two polymers by providing a favorable enthalpic effect via ionic interactions.
  • the oxidized cellulose ester thermoplastic compatibilizers are anticipated to improve the interfacial adhesion in cellulose ester natural fiber composites by providing a favorable enthalpic effect via ionic interactions.
  • the oxidized cellulose ester thermoplastic compatibilizers will increase the biodegradation rate of the blend or composite.
  • the preferred cellulose ester interpolymers are anionic, cationic, or zwitterionic C 2 -C 12 cellulose esters. More preferred cellulose ester interpolymers are anionic C 2 -C 4 cellulose esters having an acid number from about 40 to about 120. The most preferred anionic cellulose esters have an acid number from about 40 to about 90 and the substitutent type matches the neutral cellulose ester component in the polymer blend or composite.
  • the anionic cellulose esters can be used in either the acid form or when the anionic functionality has been neutralized salt.
  • the anionic cellulose ester is neutralized with a base selected from NaOH, KOH, Ca(OH) 2 , CaCO 3 , Ca(OAc) 2 , Mg(OH) 2 , MgCO 3 , or Mg(OAc) 2 .
  • the anionic cellulose ester has been neutralized and is incorporated into the blend or composite as the Ca or Mg salt.
  • the cellulose ester interpolymers of the invention can improve the compatibility in blends and the interfacial adhesion in composites.
  • the amount of the oxidized cellulose ester is from about 1 to about 15 wt % based on total weight of the mixture. In another embodiment, the amount of oxidized cellulose ester is from about 2 to about 5 wt % based on total weight of the mixture.
  • the neutral cellulose esters that can be used with the oxidized cellulose ester thermoplastic compatibilizer are secondary cellulose esters such as cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate. These cellulose esters are commercially available from Eastman Chemical Company, Inc., Kingsport, Tenn., U.S.A.
  • the neutral cellulose esters useful in the present invention have a Mw from about 5,000 to about 400,000 as measured by GPC. In another embodiment, the Mw is from about 100,000 to about 300,000. In a further embodiment, the Mw is from about 125,000 to about 250,000. In one embodiment, the DS of the neutral cellulose esters useful herein is from about 0.7 to about 3.0. in another embodiment, the DS is from about 1.7 to about 2.8. In a further embodiment, the DS is from about 1.9 to about 2.6. The preferred Mw and DS depend upon the application in which the cellulose esters are used. In certain cases, the DS of each acyl substituent will influence the properties of cellulose mixed ester. Examples of esters of cellulose include cellulose triacetate (CTA), cellulose acetate (CA), cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), and the like.
  • CTA cellulose triacetate
  • CA cellulose acetate
  • CAP cellulose acetate propionate
  • the second polymer component in the polymer blends containing the oxidized cellulose ester thermoplastic compatibilizer is selected from polyesters, polycarbonates, cellulose esters, polyalkanoates, polyamides, polyesteramides.
  • the oxidized cellulose ester thermoplastic compatibilizer and the neutral cellulose esters can be in the form of a powder, bead, pellet, or fiber prior to incorporation into natural fiber composites. Most preferred is when the oxidized cellulose ester thermoplastic compatibilizer and the neutral cellulose esters are in the form of a fiber.
  • the oxidized cellulose ester thermoplastic compatibilizer and the neutral cellulose esters are plasticized either in the fiber form prior to incorporation into the composite or during formation of the composite.
  • preferred plasticizers include phthalates (e.g. diethyl or dibutyl phthalate), glycerol, triacetin, citrate esters (eg. triethylcitrate), aliphatic diesters (e.g. dioctyl adipate), phosphates (e.g. triphenyl phosphate), low molecular weight polyethylene glycols, esters of polyethylene glycols, and carbohydrate or polyol esters (See U.S. Ser. No. 10/340,012, filed Jan.
  • plasticizers are carbohydrate or polyol esters. Selection of the proper plasticizer and the amount of plasticizer is based upon the compatibility of the plasticizer with the cellulose ester and on the desired properties in the finished part. In this regard, it is important to note that the compatibility of each plasticizer will vary with each cellulose ester. For example, dioctyl adipate has poor compatibility with cellulose acetates, but good compatibility with most cellulose acetate butyrates.
  • the natural fibers of the composite structure comprise hemp, sisal, flax, kenaf, cotton, abaca, jute, kapok, papyrus, ramie, coconut (coir), wheat straw, rice straw, hardwood pulp, softwood pulp, and wood flour. More preferably, the natural cellulose fiber is selected from the group consisting of hemp, sisal, flax, kenaf, cotton, jute and coir. A suitable fiber length for the natural cellulose fiber component of this invention would be 0.01 to 10.2 cm.
  • the composite structure be comprised of about at least 50 wt % natural fiber. More preferable is when the natural fiber is from about 60 to about 75 wt % with the balance being comprised of the oxidized cellulose ester thermoplastic compatibilizer and the neutral cellulose esters.
  • compositions those skilled in the art will understand that the most preferred compositions, the preferred method of forming the composites, and the preferred processing conditions will depend on the intended applications and desired physical properties. As such, a broad composition range and processing window is anticipated.
  • This invention also relates to the use of the cellulose ester interpolymers of this invention as film forming agents, thickening agents, rheology modifiers, wetting agents, and dispersing agents in personal care formulations.
  • personal care formulations include, but are not limited to, hair care, nail polish, skin gloss and makeup, lipstick and lip gloss, deodorants, mascara, and eyeliner formulations.
  • the preferred cellulose ester interpolymers are anionic, cationic, or zwitterionic C 2 -C 12 cellulose esters. More preferred cellulose ester interpolymers are anionic, cationic, or zwitterionic C 2 -C 4 cellulose esters. The more preferred oxidized cellulose esters are anionic C 2 -C 4 cellulose esters having an acid number of about 40 to about 120. Those skilled in the art will recognize that the most preferred oxidized cellulose esters will be determined by the particular personal care formulation and the intended use.
  • carboxyl groups of the preferred cellulose ester interpolymers are neutralized to provide increased solubility or clarity of the dispersion, and to provide continuous film formation.
  • Neutralization can be accomplished by using an inorganic base such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, or combinations thereof.
  • Organic bases may also be used and include for example, monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-methyl propanol (AMP), monoisopropaolamine, triisopropanolamine, and combinations thereof.
  • the degree of neutralization (percentage of acid groups that are neutralized with base) varies depending on the other ingredients in the personal care formulations, and the intended function and/or performance characteristics of the personal care formulations. Generally, the degree of neutralization is from about 20 to 100%. The preferred neutralization is from about 40 to 90%; and most preferred is from about 50 to 80%.
  • the resins that can be used with preferred cellulose ester interpolymers in personal care compositions can be substantially hydrophobic.
  • hydrophobic resins include, but are not limited to, neutral cellulose esters such as cellulose acetate propionate or cellulose acetate butyrate, waxes; silicones; fluorocarbons; UV absorbers; photoinitiators; chlorinated and nonchlorinated polyolefins; hydroxy-functional resins such as acrylics, polyesters, and polyethers; acrylate-functional resins such as acrylated acrylics, acrylated polyesters, acrylated polyethers, acrylated polyurethanes, and acrylated epoxies; amine-modified acrylated acrylics, polyesters and polyethers; unsaturated polyesters; allyl functional polymers; aminoplast resins, and the like.
  • additives include, but or not limited to, plasticizers, coalescing agents, silicones, emollients, emulsifiers, lubricants, penetrants such as various lanolin compounds, protein hydrolysates, or other protein derivatives, viscosity increasing and decreasing agents, ethylene adducts and polyoxyethylene cholesterol, dyes, tints and other colorants, perfumes or fragrances, preservatives, antifoaming agents, chelating agents, polymers and resins, conditioners, and the like.
  • additives that can be included in personal care formulations involving the cellulose ester interpolymers of the present invention include, but are not limited to, polysiloxane polyether copolymers, polysiloxane polydimethyl dimethylammonium acetate copolymers, acetylated lanolin alcohols, lauryl dimethylamine oxide, a lanolin-derived extract of sterol ester, lanolin alcohol concentrate, an isopropyl ester of lanolin fatty acid, sulfur rich amino acid concentrate, oleyl alcohol, stearyl alcohol, stearamidopropyl dimethyl myristyl acetate, a polyol fatty acid, a fatty amido amine, guar hydroxypropyltrimethyl ammonium chloride, cetyl/stearyl alcohol, keratin protein derivatives, isostearamidopropyl dimethylamine, stearamidopropyl dimethylamine, an amino functional silicone, ethoxylated
  • plasticizer additives include, but or not limited to, glycols, adipic esters, citrate esters, phthalate esters, carbohydrate or polyol esters, epoxidized vegetable oils, glycerine as well as polymeric plasticizers.
  • plasticizers in accordance with the invention are, for example, diethylhexyladipate, dibutyl phthalate, dibutyl adipate, diethyl phthalate, diisobutyl adipate, diisononyl adipate, n-butyl benzyl phthalate, 1,3-butylene glycol/adipic acid polyester, tricresyl phosphate, benzyl benzoate, triphenyl phosphate, butyl stearate, triethyl citrate, tributyl citrate, tributyl acetyl citrate, camphor, epoxidized soybean oil, propylene glycol adipate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TXIB), 2-amino-2-methyl propanol, and dibutyl sebacate.
  • Other plasticizers include: Dimethicone copolyol
  • additives include but are not limited to emulsifiers such as ethoxylated fatty alcohols and esters, ethoxylated glycerides, dimethicone copolyol esters, glyceryl esters, hydrogenated fatty glycerides, and the sodium salts of fatty acids.
  • emulsifiers such as ethoxylated fatty alcohols and esters, ethoxylated glycerides, dimethicone copolyol esters, glyceryl esters, hydrogenated fatty glycerides, and the sodium salts of fatty acids.
  • Preservatives such as benzyl alcohol, methyl paraben, propyl paraben and imidazolidinylurea may also be used.
  • Viscosity increasing agents that may be used include, methyl vinyl ether/maleic anhydride copolymer cross linked with 1,9-decadiene, carbomers, acrylates/alkyl acrylate cross polymers, the diethanolamide of a long chain fatty acid, fatty alcohols (for example, stearyl alcohol), cellulose gum, sodium chloride, and sodium sulfate.
  • Viscosity decreasing agents that may be used include, for example, ethyl alcohol, glycerin, propylene glycol, and ethoxydiglycol.
  • the pH of personal care formulations may be adjusted using pH adjusting agents such as citric acid, succinic acid, sodium hydroxide, and triethanolamine.
  • Colorants for use in personal care formulations are, for example, any of the Food, Drug and Cosmetics (FD&C) or Drug and Cosmetics (D&C) dyes.
  • Bleaching agents such as hydrogen peroxide, perborate salts, persulfate salts, and percarbonate salts may also be used.
  • Perfume oils are also commonly found in many personal care products and may be used here.
  • Chelating agents such as ethylenediamine tetraacetic acid (EDTA), may also be used.
  • the solvents that are useful for the personal care formulations of the present invention may be water, organic solvents, or mixtures thereof.
  • the preferred oxidized cellulose ester is dissolved in a compatible solvent, the resins or additives to be incorporated are added, the oxidized cellulose ester is neutralized to a given percent neutralization, and the solution inverted from a solvent continuous phase to an aqueous continuous phase.
  • the cellulose ester interpolymers are also functioning as a dispersing agent in the personal care formulation.
  • the preferred oxidized cellulose ester can be added directly to a solution containing water, base, and organic solvent to obtain a solution.
  • organic solvents include, but are not limited to, alcohols, ketones, alkyl esters, polyols, ethers, aromatic hydrocarbons, and mixtures thereof.
  • preferred organic solvents include, but are not limited to, ethanol, propanol, isopropanol, acetone, 2-butanone, methyl acetate, ethyl acetate, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, diethylene monoethyl ether, toluene, xylene, and mixtures thereof.
  • interpolymers include polymers comprising two or more different monomer units. Interpolymers include copolymers and terpolymers. Further, interpolymer includes graft copolymers comprising a cellulose polymer grafted to another polymer such as, but not limited to, a polyethylene glycol.
  • a random distribution of carboxy groups on a cellulose polymer is defined as a cellulose polymer where the probability that an anhydroglucose unit having a C6 carboxy group is flanked on either or both by anhydroglucose units having a C6 carboxy group is unpredictable.
  • a C6 carboxy group refers to the 6 position of an anhydroglucose unit being a —CO 2 H group wherein the —CO 2 H includes the free acid, salts of alkali earth metals, and ammonium and substituted ammonium salts.
  • a C6 formyl group refers to the 6 position of an anhydroglucose unit being a —C(O)H group.
  • a stable form of a cellulose ester interpolymer is one that is stable to air hydrolysis, and capable of being isolated, characterized, and stored as a neat compound. Further, in this context, in one embodiment, the term “stable” means that it may be isolated and stored for up to six months with less than 5% hydrolysis of acyl substituents.
  • an amino substituted cyclic nitroxyl derivative refers to compounds having carbocyclic rings comprising a nitroxyl group as one of the members of the ring, where no protons are alpha to the nitroxyl group, and the amino substitutent is located at a position on the carbocyclic ring other than alpha to the nitroxyl group.
  • the size of the carbocyclic ring is not particularly limited so long as the amino substituted cyclic nitroxyl derivative is operable to oxidize the C6 position of anhydroglucose units of a cellulose or cellulose ester interpolymer.
  • the carbocyclic ring contains six atoms.
  • the carbocyclic ring contains 5 atoms.
  • the amino group may comprise an amine or a substituted amine wherein the substituent may comprise an alkyl group or a C 2 -C 12 acyl group.
  • the amino substituted cyclic nitroxyl derivative is a 4-amino substituted 2,2,6,6-tetramethyl piperidin-1-oxyl derivative.
  • the amino substituted cyclic nitroxyl derivative is 4-amino 2,2,6,6-tetramethyl piperidin-1-oxyl.
  • the amino substituted cyclic nitroxyl derivative is a 4-(C 1 -C 4 acylamido)-2,2,6,6-tetramethylpiperidin-1-oxyl. In another embodiment, the amino substituted cyclic nitroxyl derivative is 4-acetamido-2,2,6,6-tetramethylpiperidin-1-oxyl.
  • anhydroglucose units having C2, C3, and/or C6 positions “in the alcohol oxidation state” include anhydroglucose units where the position in the alcohol oxidation state is not an aldehyde, ketone, or carboxy group.
  • positions in the alcohol oxidation state include hydroxyl groups and hydroxy group derivatives such as alkyl ethers and O-acyl groups.
  • AN means acid number
  • MEK means methyl ethyl ketone
  • PM acetate means propylene glycol monomethyl ether acetate
  • diacetone alcohol means 4-hydroxy-4-methyl-2-pentanone
  • MPK means methyl propyl ketone
  • EB means ethylene glycol monobutyl ether
  • EP means ethylene glycol monopropyl ether
  • PM means propylene glycol monomethyl ether
  • PB propylene glycol monobutyl ether
  • EB acetate means ethylene glycol monobutyl ether acetate
  • PP means propylene glycol monopropyl ether
  • 2-EH acetate means 2-ethyl-1-hexanol acetate
  • EEP means ethyl 3-ethoxypropionate
  • MIBK means methyl iso-butyl ketone
  • MAK means methyl amyl ketone
  • an “alkyl” group unless noted otherwise, preferably refers to a C 1 -C 12 straight chain hydrocarbon group.
  • aryl preferably refers to groups such as phenyl, napthyl, phenanthryl, biphenyl, etc.
  • hydroxymethylene refers to a group of the formula —CH 2 OH.
  • alkylenearyl preferably refers to a C 1 -C 12 alkylene group having an aryl group attached.
  • the internal reaction temperature reached 37° C.
  • the reaction temperature was increased to 58° C.
  • the reaction mixture became a homogeneous solution 6.8 h after adding the cellulose.
  • the reaction temperature was maintained at 58° C. for an additional 4 h after the homogeneous solution was obtained.
  • the reaction mixture was diluted with 500 mL of acetic acid before pouring slowly with high agitation into 5 L of H 2 O. This gave a fine white powder, which was isolated by filtration and dried.
  • FIG. 1 shows the 1 H NMR spectra for Examples 1-4.
  • the resonances due to the C6 protons of the carbon bearing a formate or acetate substitutent are labeled as 6 F and 6A.
  • This data illustrates that as the number of equivalents of formic acid increases, the DS of formate and the ratio of C6 formate/acetate increases.
  • the concentration of formic acid is held constant and the amount of Ac 2 O is decreased (Example 5), the DS of formate and the ratio of C6 formate/acetate remains virtually unchanged.
  • This data demonstrates that the concentration of formic acid is one of the features that control the DS of formate and selectivity at C6 for formate.
  • cellulose acetate formates were prepared using identical conditions except for the reaction temperature. Shortly after obtaining a homogeneous reaction mixture, which is indicative of full esterification of the cellulose, the first sample was removed and isolated. In each case, cellulose acetate formates were obtained (entries 6-A, 7-A, 8-A) with weight-average molecular weights ranging from about 300,000 to about 100,000 and a formate DS from about 0.9 to about 1.05.
  • Tables 2, 3 and 4 shows the change in molecular weight, formate DS and acetate DS when the reaction is maintained at different temperatures after reaching the triester stage. At 65° C.
  • Proton NMR indicated that the CP had a DS of 1.67.
  • the Mw of this CP was 93,420.
  • the Tm taken from the first scan DSC spectra was 229° C. and the second scan Tg was 180° C.
  • the RDS at the 6, 3, and 2 positions were 0.26, 0.69, and 0.71, respectively, indicating that the CP contained a high amount of the 2,3-dipropionate substituted monomer.
  • Example 17-A is the first aliquot taken 4 h after beginning the peracetic acid addition (15 min after completion of the peracetic acid addition). As can be seen, Example 17-A has an acid number of 97.5, the apparent DS has increased to 2.0, and the observed Mw is now 426,173. As the reaction progresses, the acid number and the DS remains relatively constant while the Mw decreases reaching 43,061 for Example 17-D. The relatively constant DS indicates that little or no hydrolysis of the acetyl substitutent is occurring under these reaction conditions.
  • Example 18-A The 1 H NMR spectra for Example 18-A (7.4 h at 40° C.) and Example 19-A (2.9 h at 60° C.).
  • the presence of a resonance at about 9.5 ppm for Example 18-A corresponds to that of an aldehyde. This resonance is absent in the 1 H NMR spectrum for 19-A.
  • Aldehydes in the presence of alcohols act as cross-linking points via formation of an acetal and can lead to the observed higher molecular weights for the examples in Table 8.
  • the absence of an aldehyde resonance in the 1 H NMR spectrum for 19-A indicates oxidation of aldehyde to carboxy before the aldehyde can cross link.
  • Cellulose acetate (prepared according to the general methods of Examples 6-8 and 12) was oxidized at 50° C. according to the general procedure of Example 17.
  • FIG. 3 shows the 13 C NMR C6 carbon resonances for Examples 20-23.
  • the resonances corresponding to C6 substituted (ca. 63.5 ppm) and unsubstituted (ca. 59 ppm) carbons are indicated.
  • oxidation using NHAcTEMPO Example 23
  • Reactions involving TEMPO Examples 20-22
  • Oxidation of this CA using NaBr as the primary oxidant provided an anionic CA with an acid number of 86 (Example 24). Substitution of NaBr with other metal halides such as NaCl or NaOCl (Examples 25 and 26) also led to significant oxidation of this CA. Salts or acids based on sulfur gave oxidized CA with low acid numbers (Examples 37-39). Example 37 was particularly surprising as the prior art teaches that strong acids such as H 2 SO 4 are critical components in TEMPO based oxidations of polysaccharides. Examples 27-32 demonstrate that Mn salts are useful as primary oxidants in the oxidation of polysaccharides such as cellulose esters. That is, it is possible to have halogen free oxidations.
  • Example 28 involving Mn(OAc) 3 which gave an acid number of 39.8.
  • the salt does not contain a halogen. Oxidation of acetate would lead to peracetic acid which, in the absence of a good primary oxidant, gives only low levels of oxidation. Hence, the observed increase in acid number is due to the Mn.
  • Examples 29 and 30 are of particular interest.
  • KMnO 4 is a known oxidant of polysaccharides but is also known that high levels of KMnO 4 are required and that this leads to nonselective oxidations with significant loss in molecular weight.
  • Example 29 demonstrates that when used with NHAcTEMPO according to the methods of the present invention, KMnO 4 can be used catalytically to provide a cellulose ester with high levels of oxidation and good molecular weight. In comparison, in the absence of NHAcTEMPO (Example 32), a much lower acid number and molecular weight is obtained. Examples 33-36 demonstrate that other metal salts such as Mg, Cu, and Fe can also be used as primary oxidants in the oxidation of cellulose esters.
  • This example demonstrates that primary oxidants other than NaBr are useful in the oxidation of cellulose esters by the methods of the present invention.
  • metal salts based on Mn, Mg, Fe, and Cu for halogen free oxidations.
  • this example shows that the presence of a strong acid such as H 2 SO 4 , is not necessary for the oxidation of polysaccharide esters as suggested in the prior art. In this case, the presence of the strong acid resulted in essentially no oxidation of the cellulose ester.
  • the data in Table 12 illustrates a number of points.
  • a primary oxidant is not necessary to obtain oxidation.
  • addition of even a small amount of NaBr increased the level of oxidation (cf. Examples 43 and 44) relative to when none was used.
  • the acid number and the molecular weight of the oxidized cellulose ester can be controlled by varying the amount of NaBr while maintaining a constant temperature and concentration of NHAcTEMPO.
  • Cellulose acetate propionate and cellulose acetate butyrate commercially available from Eastman Chemical Co. as CAP504 and CAB553, were oxidized at 50° C. according to the general procedure of Example 17 using 1.0 eqs PAA, 0.005 eqs of NaBr, and 0.075 eqs NHAcTEMPO.
  • CAP 504 propionic acid was substituted for acetic acid.
  • CAB 553 butyric acid was substituted for acetic acid.
  • the oxidized cellulose esters were isolated by precipitation in 5% aqueous acetic acid. The results of these experiments are summarized in Table 14.
  • Water activated cellulose (10 g) was suspended in 400 g of a mixture of acetic acid/H 2 O (85/15, wt./wt.) containing NHAcTEMPO (0.99 g) and NaBr (0.032 g) at 50° C.
  • the oxidation was started by slowly adding 25.9 mL of a 32% peracetic acid solution with stirring, in 3 hours, to the mixture.
  • the oxidized cellulose was isolated, after 4.5 hours of reaction, by filtration, washed, and dried at 50° C. in a vacuum oven.
  • the oxidized cellulose was acetylated with acetic anhydride using sulfuric acid as catalyst. Specifically, oxidized cellulose (10 g) was activated with water, dewatered with acetic acid, and then suspended in a mixture of acetic acid (100 g) and acetic anhydride (28 g) at 13-15° C. The esterification was started by adding a mixture of sulfuric acid (0.75 g) and acetic acid (20 g) to the above cold cellulose, acetic acid and acetic anhydride mixture with vigorous mixing. This reaction mixture was kept at 20 to 23° C. for about 20 to 30 min follow by heating it at 50° C. until a viscous solution was obtained.
  • Cellulose (Placetate F) was first activated with 10% aqueous NaOH at 0 to 10° C. for 10 to 20 min. The NaOH solution was then removed from cellulose by filtration and washing with distilled water. The pH of this activated cellulose was then adjusted to 10.8 to 10.9 using 0.5 M NaOH. The oxidation was started by slowly adding 11.5% solution of NaOCl (85 ml) to a mixture of activated cellulose (10 g), TEMPO (0.1 g), NaBr (3.2 g) and distilled water (400 g) in a 3-necked round bottle flask with stirring. The reaction temperature was 25° C., and the pH of the reaction mixture was kept at 10.8 to 10.9 with 0.5 M NaOH.
  • Cellulose was in solution at the end of the addition of NaOCl solution (120 min.).
  • the oxidized cellulose was recovered by precipitation from ethanol, washed with ethanol and dry at 50° C. in a vacuum oven. After drying, the acid number for the oxidized cellulose was determined to be 133.
  • a regioselectively substituted cellulose ester can provide an oxidized cellulose acetate with a higher acid number than that obtained from the equivalent randomly substituted cellulose acetate.
  • the reaction mixture was poured into an Omni blender and a mixture of H 2 O and ice was added. After mixing, the oxidized CA precipitated. The product was washed twice with water before washing with ethanol. Drying in vacuo at 60° C. for 65 h gave a white solid (84% yield). After drying, the product was quite difficult to dissolve in most solvents due to cross-linking via acetal formation between the newly formed aldehyde and unreacted hydroxyls that are present in the cellulose ester. Nevertheless, the 1 H NMR of the product (DMSO-d 6 , reveals the resonances due to the desired aldehyde groups (9-10 ppm). The resonances centered near 6 ppm are believed to be due to acetals formed by reaction of unreacted hydroxyls with the aldehyde functionality.
  • reaction mixture After addition of the sulfuric acid mixture, the reaction mixture was held at 70° C. for the entire reaction time. After 12 h reaction time, 240 g of deionized water was added. After 24 h reaction time, an additional 400 g of deionized water was slowly added. After 36 h reaction time, a final addition was added consisting of 1560.0 g of acetic acid, 72.0 g of butyric acid, and 324.0 g of deionized water, and 152.8 g of magnesium acetate tetrahydrate. For characterization purposes, a small portion of the resulting CAB was isolated by adding the reaction solution to deionized water, filtering, and washing the solid with water and drying.
  • the remaining CAB reaction mixture was drained from the flask and stored at 10° C. until used in oxidation reactions.
  • the weight-average molecular weight (GPC) was 104,681.
  • cellulose esters such as CAB can be hydrolyzed in acidic aqueous media to produce randomly substituted cellulose esters with high hydroxyl content.
  • Oxidation of this CAB using different primary oxidants produced oxidized CAB with a range of acid numbers (11 to 98) and weight-average MW (ca. 5000 to 36000).
  • acid numbers 11 to 98
  • weight-average MW ca. 5000 to 36000.
  • Example 62 The procedure of Example 62 was used to produce a CAB381 having a high hydroxyl content. This example is different in that the reaction temperature was maintained at 71° C. and the composition of the liquids added at 36 h was 990 g of acetic acid, 48 g of butyric acid, and 560 g of deionized water, and 51 g of magnesium acetate tetrahydrate.
  • the weight-average molecular weight (GPC) was 66,097.
  • the CAB produced above was oxidized by the general procedure of Example 17 using 0.075 eq of NHAcTEMPO and 0.75 eq of sodium bromide.
  • the product obtained had an acid number of 104 (mg KOH/g) and a weight-average molecular weight of 4847.
  • CAB can be hydrolyzed in acidic aqueous media to produce a randomly substituted CAB with high hydroxyl content. Oxidation of this CAB using 0.75 eqs of NaBr produced an oxidized CAB with a high acid number and a low weight-average molecular weight.
  • Magnesium stearate powder (0.04 g) which had been dispersed in carbon black (0.13 g carbon black to 1.0 g magnesium stearate) was added to the powder and mixed until an even pale gray color was achieved.
  • Tablets (0.34-0.37 g) were pressed individually using a tablet press at 5000 psi.
  • 6.0 g of cellulose diacetate (CA-398-30) powder was milled with 1.5 g NF Grade aspirin with 0.04 g Mg stearate/carbon black added.
  • Tablets (0.32-0.37 g) tablets were also pressed at 5000 psi.
  • the dissolution test was completed using a USP #2 calibrated apparatus with Teflon paddles. Buffer solutions were degassed at 41° C. through a 0.45 micron nylon filter and held under vacuum for an additional 5 minutes. After adding the solutions to the dissolution vessels, the solutions were held at 37.3° C. for 30 minutes to achieve constant temperature.
  • the tablets were added to 900 ml of USP 1.2 pH buffer or to 900 ml of USP pH 6.8 buffer. The tablets were weighted down with a Varian 3-pronged capsule weight. At the beginning of each experiment, the tablets were allowed to sink to the bottom of the 1000 ml vessel, the stirrers were turned on at 50 rpm and samples taken as a function of time, using polypropylene syringes.
  • the samples were filtered through 0.45 micron filters and immediately analyzed for the amount of aspirin in the solution using a Varian UV-Vis Spectrophotometer and quartz absorption cells.
  • the wavelengths for measuring the amount of salicylic acid at pH 1.2 and 6.8 was 278 nm and 235, respectively.
  • Each set of experiments had appropriate standards for reference for quantitative analysis.
  • the oxidized cellulose acetate (CAOX) tablets formed cracks at pH 1.2 but retained their original shape at pH 6.8. After 3 hours, the CAOX tablets in pH 6.8 buffer solution had almost completely disappeared leaving a clear solution. At pH 1.2, the CAOX tablets retained the same shape that they had achieved after 10 minutes in the buffer solution. In contrast to both, the CA-398-30 tablets did not change shape through the course of the experiment at pH 1.2 or pH 6.8.
  • FIG. 5 summarizes the results of these experiments.
  • pH 1.2 After 200 min at pH 1.2, only 23% of the maximum amount of aspirin had been released from the intact CAOX tablets. In contrast, at pH 6.8 84% of the maximum available aspirin was released into the media. In the case of the CA398 tablets, 27% and 45% of the available aspirin was released at 200 min at pH 1.3 and 6.8 respectively.
  • the CAOX has low solubility at pH 1.2 and is sufficiently hydrophobic to prevent significant release of the highly water soluble aspirin by diffusion.
  • pH 6.8 the CAOX dissolved releasing the drug from the matrix.
  • the tablets made from cellulose acetate remained intact at this pH 6.8 and only 45% of the drug was released by a diffusion controlled process.
  • This example illustrates that the oxidized cellulose esters of the present invention can be used to form tablets by compression molding. Because the tablet structure is sensitive to pH, lowered amounts of the drug is released at pH 1.2 (normal stomach pH) while at higher pH (the normal pH gradient of the small intestine is 4.5-7.2), high amounts of the drug is released.
  • pH 1.2 normal stomach pH
  • pH 4.5-7.2 the normal pH gradient of the small intestine is 4.5-7.2
  • This type of formulation is particularly useful in providing controlled release of drug actives in the intestine as opposed to the harsh environment of the stomach. That is, the oxidized cellulose esters of this invention act as release rate modifiers.
  • Four independent aqueous CA solutions were prepared by this process. Concurrently, independent solutions containing 40-41 mg of ritonavir, anastrozole, tamoxifen, or letrozole were prepared by dissolving each drug in 5 mL of absolute ethanol. Each of these drugs has poor water solubility.
  • the ethanol solution of each drug was then added slowly to the aqueous CA solutions previously prepared. After addition of each drug solution, the pH of each solution was measured and found to be 4.0-4.3. The oxidized CA:drug solutions were then freeze dried which provided white powders of each mixture.
  • Solutions of each of the oxidized CA:drug mixtures were prepared in Millipore water (23.0-26.5 g/L). All of the samples were filtered thru 0.45 micron syringe filters before measurement. The pH of each solution after filtration ranged from 3.9-4.1. Solutions of each of the oxidized CA:drug mixtures were also prepared in 50/50 ethanol/Millipore water. All of the oxidized CA:drug mixtures dissolved in the ethanol/water mixture providing clear solutions thus allowing determination of the maximum amount of drug that can be observed with each sample. All samples were immediately analyzed for the amount of drug in the solution using an UV-Vis Spectrophotometer.
  • Table 18 Also shown in Table 18 are the pKa for each of these basic drugs.
  • the pH of the formulations and of the aqueous drug solutions were above the pKa of the drug. That is, these basic drugs were not significantly ionized.
  • the % drug solubilized was relatively low.
  • the pH of the formulation and of the aqueous drug solution were very near the pKa of anastrozole. In this case the % drug solubilized is high while Sw/So is relatively low.
  • the pH of the formulation and of the aqueous drug solution is ca.
  • the cellulose ester interpolymers of the present invention can serve to modify the solubility of drugs in aqueous media. Without wishing to be bound by theory, it is believed that the cellulose ester interpolymers modifies the solubility of drugs by changing the concentration of the ionized species and through specific interactions between the drug and oxidized cellulose ester interpolymer.
  • Topac Inc. gelatin capsules (#3, 0.30 ml) with a lock-ring design were filled with approximately 0.17-0.19 g USP grade pure aspirin.
  • Charcoal powder was used as a colorant to determine whether or not the capsules were being evenly coated. The coated capsules were allowed to air dry overnight.
  • the dissolution test was completed using a USP #2 calibrated apparatus with Teflon paddles. Buffer solutions were degassed at 41° C. through a 0.45 micron nylon filter and held under vacuum for an additional 5 minutes. After adding the solutions to the dissolution vessels, the solutions were held at 37.3° C. for 30 minutes to achieve constant temperature.
  • the capsules were added to 900 mL of USP 1.2 pH buffer or to 900 mL of USP pH 6.8 buffer.
  • the tablets were weighted down with a Varian 3-pronged capsule weight. At the beginning of each experiment, the tablets were allowed to sink to the bottom of the 1000 mL vessel, the stirrers were turned on at 50 rpm and samples taken as a function of time, using polypropylene syringes.
  • the experiment was run continuously for 21 hours.
  • the samples were filtered through 0.45 micron filters and immediately analyzed for the amount of aspirin in the solution using a Varian UV-Vis Spectrophotometer and quartz absorption cells.
  • the wavelengths for measuring the amount of aspirin acid at pH 1.2 and 6.8 were 280 nm and 298 nm, respectively.
  • Each set of experiments had appropriate standards for reference for quantitative analysis.
  • the capsules coated with CA398-10 did not appear to physically change during the course of the experiment. As illustrated in FIG. 6 , less than 2% of the aspirin dissolved at both pH 1.2 and pH 6.8 over the course of the experiment. After 300 min at pH 1.2 and 6.8, less than 0.1% of the available aspirin was released into the media.
  • This example demonstrates the use of oxidized cellulose interpolymers as an enteric coating to prevent drug dissolution at pH 1.2 (pH of the stomach) while permitting rapid drug release at the normal pH of the small intestine (4.5-7.2). Because the capsule coated with the cellulose ester interpolymer is sensitive to pH, lowered amounts of the drug is released at normal stomach pH while at intestinal pH, high amounts of the drug is released. That is, the cellulose ester interpolymers of this invention function as enteric coatings.
  • Four independent aqueous CA solutions were prepared by this process. Concurrently, independent solutions containing 40-41 mg of ritonavir, anastrozole, tamoxifen, or letrozole were prepared by dissolving each drug in 5 mL of absolute ethanol. Each of these drugs has poor water solubility.
  • the ethanol solution of each drug was then added slowly to the aqueous CA solutions previously prepared. After addition of each drug solution, the pH of each solution was measured and found to be 4.0-4.3. The oxidized CA:drug solutions were then freeze dried which provided white powders of each mixture.
  • FIG. 7 summarizes the results obtained in this experiment.
  • the resulting formulation was tested for sag resistance using ASTM D4400-898.
  • the paint showed significantly improved sag resistance relative to a control which did not contain the oxidized cellulose ester.
  • CAB refers to cellulose acetate butyrate available from Eastman Chemical Company).

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